MLCT State Research Articles

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

AbstractIron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.

Neutral Cyclometalated Iridium(III) Complexes Bearing Substituted N-Heterocyclic Carbene (NHC) Ligands for High-Performance Yellow OLED Application.

The synthesis, crystal structure, and photophysics of a series of neutral cyclometalated iridium(III) complexes bearing substituted N-heterocyclic carbene (NHC) ancillary ligands ((C∧N)2Ir(R-NHC), where C∧N and NHC refer to the cyclometalating ligand benzo[h]quinoline and 1-phenylbenzimidazole, respectively) are reported. The NHC ligands were substituted with electron-withdrawing or -donating groups on C4' of the phenyl ring (R = NO2 (Ir1), CN (Ir2), H (Ir3), OCH3 (Ir4), N(CH3)2 (Ir5)) or C5 of the benzimidazole ring (R = NO2 (Ir6), N(CH3)2 (Ir7)). The configuration of Ir1 was confirmed by a single-crystal X-ray diffraction analysis. The ground- and excited-state properties of Ir1-Ir7 were investigated by both spectroscopic methods and time-dependent density functional theory (TDDFT) calculations. All complexes possessed moderately strong structureless absorption bands at ca. 440 nm that originated from the C∧N ligand based 1π,π*/1CT (charge transfer)/1d,d transitions and very weak spin-forbidden 3MLCT (metal-to-ligand charge transfer)/3LLCT (ligand-to-ligand charge transfer) transitions beyond 500 nm. Electron-withdrawing substituents caused a slight blue shift of the 1π,π*/1CT/1d,d band, while electron-donating substituents induced a red shift of this band in comparison to the unsubstituted complex Ir3. Except for the weakly emissive nitro-substituted complexes Ir1 and Ir6 that had much shorter lifetimes (≤160 ns), the other complexes are highly emissive in organic solutions with microsecond lifetimes at ca. 540-550 nm at room temperature, with the emitting states being predominantly assigned to 3π,π*/3MLCT states. Although the effect of the substituents on the emission energy was insignificant, the effects on the emission quantum yields and lifetimes were drastic. All complexes also exhibited broad triplet excited-state absorption at 460-700 nm with similar spectral features, indicating the similar parentage of the lowest triplet excited states. The highly emissive Ir2 was used as a dopant for organic light-emitting diode (OLED) fabrication. The device displayed a yellow emission with a maximum current efficiency (ηc) of 71.29 cd A-1, a maximum luminance (Lmax) of 32747 cd m-2, and a maximum external quantum efficiency (EQE) of 20.6%. These results suggest the potential of utilizing this type of neutral Ir(III) complex as an efficient yellow phosphorescent emitter.

Helicene Bis(pyrazol‐1‐yl)pyridine Ligands for Luminescent Transition‐Metal Complexes

We describe herein the synthesis of 2,6‐bis(pyrazol‐1‐yl)pyridine (1‐bpp) ligands substituted by helicene units in the 4‐position of the pyridine ring. The two‐step procedure afforded the molecules bpp[n]helicene (n = 4, 5 and 6) and methyl‐bpp[4]helicene, abbreviated as 4, 5, 6 and 4m respectively, with overall good yields. This series of ligands shows fluorescence in the violet region, with a red shift of the emission when increasing the number of aromatic rings in the helicene unit. The tridentate fluorophores have been reacted with Re(CO)5Cl and [Ru(terpy)Cl3] to prepare a series of transition metal complexes formulated as [ReI(n)(CO)3Cl] (n = 4 and 5) and [RuII(n)(terpy)](PF6)2 (n = 4, 4m, 5 and 6). The compounds [ReI(4)(CO)3Cl]·(CH2Cl2)0.5(H2O) and [RuII(4m)(terpy)](PF6)2 crystallized in the centrosymmetric space groups P21/n and P1 respectively, and thus present both M and P helicene units in their crystal structures. The absorption and emission properties of the complexes have been studied. All complexes show luminescence at 77 K in frozen DCM solution. The tricarbonyl complex [ReI(5)(CO)3Cl] shows a strong emission band with two peaks at 540 nm and 580 nm, which could be attributed to ligand‐localized π–π* phosphorescence due to the extended π system of the ligand. The heteroleptic RuII complexes show emission bands above 600 nm attributed to the terpyridine‐based 3MLCT state.

Ultrafast Photodynamics of an Azopyridine-Functionalized Iron(II) Complex: Implications for the Concept of Ligand-Driven Light-Induced Spin Change.

We report on the ultrafast photodynamics of an iron(II) complex with a photoisomerizable pentadentate azo-tetrapyridylamino ligand after irradiation with ultraviolet light. The results of femtosecond transient electronic absorption spectroscopy performed on the low-spin (LS) form of the title complex show that initial excitation of the ππ* state of the azopyridine unit in the ligand at λpump = 312 nm is followed by an ultrafast intersystem crossing (ISC) that leads to the formation of a metal-centered (MC) 5T state, in competition with the intended photoswitching of the azopyridine unit. Additional measurements carried out upon excitation of the singlet metal-to-ligand charge-transfer (1MLCT) transition at λpump = 455 nm suggest that this energy transfer occurs via an MLCT state. The resulting high-spin (HS) 5T state of the complex is metastable and recovers to the LS ground state with a time constant of ∼3 ns. The implications of these observations on the ligand-driven light-induced spin change concept are discussed.

Two Emissive Long-Lived Excited States of an Imidazole-Functionalized Ruthenium Dipyridophenazine Complex

A ruthenium(II) polypyridine-type complex based on the dipyridophenazine ligand with a directly fused imidazole unit (L1, dipyrido[3,2-a:2',3'-c]phenazine-10,11-imidazole) has been synthesized, and its electrochemical and photophysical properties have been studied. The cyclic voltammogram of [Ru(tbbpy)2(L1)]2+ (C1) (tbbpy is 4,4'-tert-butyl-2,2'-bipyridine) shows a cathodic shift of the phenazine-based reduction process compared to similar molecules, while the first detected reduction wave (-1.34 V vs Fc/Fc+) is assigned to the imidazole unit within the molecule. On the basis of the TD-DFT calculations, the strong visible absorption band exhibited by C1 is assigned to a metal-to-ligand charge transfer (MLCT) transition with a concurrent ligand-centered (LC) transition. At room-temperature, C1 features emission (Φ = 0.04) from its lowest excited states with time constants of 1.2 and 18.3 μs. These lifetimes are assigned to emission processes from the 3MLCT and 3LC state, respectively. This is the first time that a long-lived dual emission has been observed for a ruthenium(II) complex bearing a directly fused extended π-system. Furthermore, the emission of C1 is quenched upon water addition. In contrast to related compounds based on a dipyridophenazine ligand, the excited state energy is not shifted, and the lifetime is drastically decreased to 169 ns.

Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics.

Simulation of the ultrafast excited-state dynamics and elastic X-ray scattering of the [Fe(bmip)2]2+ [bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-4-pyridine] complex is presented and analyzed. We employ quantum wavepacket dynamics simulations on a 5-dimensional potential energy surface (PES) calculated by time-dependent density functional theory with 26 coupled diabatic states. The simulations are initiated by explicit inclusion of a time-dependent electromagnetic field. In the case of resonant excitation into singlet metal-to-ligand charge transfer (1MLCT) states, kinetic (exponential) population dynamics are observed with small nuclear motion. In agreement with transient optical absorption spectroscopy experiments, we observe a subpicosecond 1MLCT → 3MLCT intersystem crossing and a subsequent decay into triplet metal-centered (3MC) states on a picosecond time scale. The simulated time-resolved difference scattering signal is dominated by the 3MC component, for which the structural distortions are significant. On the other hand, excitation into 1MC states leads to ballistic (nonexponential) population dynamics with strong nuclear motion. The reason for these ballistic dynamics is that in this case, the excitation occurs into a nonequilibrium region, i.e., far from the minimum of the 1MC PES. This results in wavepacket dynamics along the principal breathing mode, which is clearly visible in both the population dynamics and difference scattering. Finally, the importance of decomposing the difference scattering into components by electronic states is highlighted, information which is not accessible from elastic X-ray scattering experiments.

Photophysical Properties and Photobiological Activities of Ruthenium(II) Complexes Bearing π-Expansive Cyclometalating Ligands with Thienyl Groups.

A new family of cyclometalated ruthenium(II) complexes [Ru(N^N)2(C^N)]+ derived from the π-extended benzo[h]imidazo[4,5-f]quinolone ligand appended with thienyl groups (n = 1-4, compounds 1-4) was prepared and its members were characterized for their chemical, photophysical, and photobiological properties. The lipophilicities of 1-4, determined as octanol-water partition coefficients (log Po/w), were positive and increased with the number of thienyl units. The absorption and emission bands of the C^N compounds were red-shifted by up to 200 nm relative to the analogous Ru(II) diimine systems. All of the complexes exhibited dual emission with the intraligand fluorescence (1IL, C^N-based) shifting to lower energies with increasing n and the metal-to-ligand charge transfer phosphorescence (3MLCT, N^N-based) remaining unchanged. Compounds 1-3 exhibited excited state absorption (ESA) profiles consistent with lowest-lying 3MLCT states when probed by nanosecond transient absorption (TA) spectroscopy with 532 nm excitation and had contributions from 1IL(C^N) states with 355 nm excitation. These assignments were supported by the lifetimes observed (<10 ns for the 1IL states and around 20 ns for the 3MLCT states) as well as a noticeable ESA for 3 with 355 nm excitation that did not occur with 532 nm excitation. Compound 4 was the only member of the family with two 3MLCT emissive lifetimes (15, 110 ns), and the TA spectra collected with both 355 and 532 nm excitation was assigned to the 3IL state, which was corroborated by its 4-6 μs lifetime. The ESA for 4 had a rise time of approximately 10 ns and an initial decay of 110 ns, which suggests a possible 3MLCT-3IL excited state equilibrium that results in delayed emission from the 3MLCT state. Compound 4 was nontoxic toward human skin melanoma cells (SKMEL28) in the dark (EC50 = >300 μM); 1-3 were cytotoxic and yielded EC50 values between 1 and 20 μM. The photocytotoxicites with visible light ranged from 87 nM with a phototherapeutic index (PI) of 13 for 1 to approximately 1 μM (PI = >267) for 4. With red light, EC50 values varied from 270 nM (PI = 21) for 3 to 12 μM for 4 (PI = >25). The larger PIs for 4, especially with visible light, were attributed to the much lower dark cytotoxicity for this compound. Because the dark cytotoxicity contributes substantially to the observed photocytotoxicity for 1-3, it was not possible to assess whether the 3IL state of 4 led to a much more potent phototoxic mechanism in the absence of dark toxicity. There was no stark contrast in cellular uptake and accumulation by laser scanning confocal and differential interference contrast microscopy to explain the large differences in dark toxicities between 1-3 and 4. Nevertheless, the study highlights a new family of Ru(II) C^N complexes where π-conjugation beyond a certain point results in low dark cytotoxicity with high photocytotoxicity, opposing the notion that cyclometalated Ru(II) systems are too toxic to be phototherapeutic agents.

A Hole Delocalization Strategy: Photoinduced Mixed-Valence MLCT States Featuring Extended Lifetimes.

Bimetallic trans-[RuII(tpm)(bpy)(μNC)RuII(L)4(CN)]2+, where bpy is 2,2'-bipyridine, tpm is tris(1-pyrazolyl)methane and L = 4-methoxypyridine (MeOpy) or pyridine (py), was examined using ultrafast vis-NIR transient absorption spectroscopy. Of great relevance are the longest-lived excited states in the form of strongly coupled photoinduced mixed-valence systems, which exhibit intense photoinduced absorptions in the NIR and are freely tunable by the judicious choice of the coordination spheres of the metallic ions. Using the latter strategy, we succeeded in tailoring the excited state lifetimes of bimetallic complexes and, in turn, achieving significantly longer values relative to related monometallic complexes. Notable is the success in extending the lifetimes, when considering the higher density of vibrational states, as they are expected to facilitate nonradiative ground-state recovery.

Long-Lived Trimetallic Complexes of Fe(II), Ru(II), and Os(II) Based on a Heteroditopic Bipyridine-Terpyridine Bridge: Synthesis, Photophysics, and Electronic Energy Transfer.

Synthesis, characterization, and investigation of photophysical and redox behaviors of a new class of homo- and heterotrimetallic complexes of composition [(bpy/phen)2Ru(dipy-Hbzim-tpy)M(tpy-Hbzim-dipy)Ru(bpy/phen)2]6+ (M = FeII, RuII, and OsII) derived from a conjugated heteroditopic bipyridine-terpyridine bridge were carried out in this work. Trimetallic RuZnRu complexes of composition [(bpy/phen)2Ru(dipy-Hbzim-tpy)Zn(tpy-Hbzim-dipy)Ru(bpy/phen)2]6+ were also synthesized in situ as their photophysical properties are of particular interest in demonstrating the absorption and emission spectra of the complexes in the presence of a metal (Zn2+) that has neither metal-to-ligand charge transfer (MLCT) nor metal-centered (3MC) states. Complexes display intense absorption bands spanning almost the entire UV and visible region. The complexes also exhibit rich electrochemical behaviors with a number of metal-centered reversible oxidation and ligand-centered reduction waves. All complexes are luminescent at room temperature, and time-resolved emission spectral studies indicate that peripheral RuII-centered emissive 3MLCT states are quantitatively quenched, by intramolecular energy transfer to the low lying 3MLCT (for central Ru and Os) or 3MC states of the FeII center (nonluminescent). Interestingly, Fe(II) does not adversely deteriorate the photophysics of the RuFeRu assembly. Thus, multicomponent complexes in the present work can serve as well-organized light-harvesting antennas as the light absorbed by multiple chromophoric subunits is efficiently channeled to the distinct component having the lowest-energy excited state.

Photophysical study of [Ru(2,2′-bipyridine)3]2+ and [Ru(1,10-phenanthroline)3]2+ encapsulated in the Uio-66-NH2 metal organic framework

Metal organic frameworks are stable porous materials that provide an excellent environment for the encapsulation of photoactive guests. The ruthenium(II) polyimine complexes, in particular, ruthenium(II) tris-(1,10-phenanthroline) (RuPhen) and ruthenium(II) tris-(2,2′-bipyridine) (RuBpy) are ideal candidates for encapsulation due to their unique photophysics. Here the excited state properties of RuPhen and RuBpy encapsulated within the zirconium oxide based MOF Uio-66 and the amine derivatized MOF Uio-66-NH2 are reported. The encapsulated complexes exhibit stabilization of the excited triplet metal to ligand charge transfer state (3MLCT) resulting in a bathochromatic shift of the emission band and extension of the emission lifetime. The introduction of an amine functional group into the Uio-66 framework gives rise to a reduction in lifetimes relative to the parent Uio-66 framework materials that may arise from perturbation to low lying singlet in character MLCT states.

Luminescent Complexes of the Trinuclear Silver(I) and Copper(I) Pyrazolates Supported with Bis(diphenylphosphino)methane.

The first example of trinuclear copper(I) and silver(I) pyrazolates adducts with a tertiary diphosphine (Ph2PCH2PPh2) retaining trimeric [MPz]3 core is reported. Despite rather strong M-P bonding, the complexes are able to undergo the dissociation of one M-P bond leading to the "merry-go-round" movement of P atoms over the M3 triangle. The copper complex displays emission from 1MLCT and 3MLCT states. The triplet and singlet states are separated by a relatively small energy gap (1080 cm-1) that triggers the thermally activated delayed fluorescence (TADF) behavior and leads to the worthy quantum yield of 41% at 298 K. The silver complex in the solid state and frozen solution shows dual emission originating from the 1IL and 3MLCT states that is dictated by the much higher energy difference between the emissive singlet and triplet as well as by the essentially different nature of these states.

Photophysical Processes in Rhenium(I) Diiminetricarbonyl Arylisocyanides Featuring Three Interacting Triplet Excited States.

We present a series of four transition-metal complexes based on the rhenium(I) tricarbonyl 1,10-phenanthroline (phen) template, with a lone ancillary arylisocyanide (CNAr) ligand to yield metal-organic chromophores of the generic molecular formula [Re(phen)(CO)3(CNAr)]+ [CNAr = 2,6-diisopropylphenyl isocyanide (1), 4-phenyl-2,6-diisopropylphenyl isocyanide (2), 4-phenylethynyl-2,6-diisopropylphenyl isocyanide (3), and 4-biphenyl-2,6-diisopropylphenyl isocyanide (4)]. This particular series features varied degrees of π-conjugation length in the CNAr moiety, resulting in significant modulation in the resultant photophysical properties. All molecules possess long-lived [8-700 μs at room temperature (RT)], strongly blue-green photoluminescent and highly energetic excited states (λmax,em = 500-518 nm; Φ = 14-64%). Each of these chromophores has been photophysically investigated using static and dynamic spectroscopic techniques, the latter probed from ultrafast to supra-nanosecond time scales using transient absorption and photoluminescence (PL). Time-resolved PL intensity decays recorded as a function of the temperature were consistent with the presence of at least two emissive states lying closely spaced in energy with a third nonemissive state lying much higher in energy and likely ligand-field in character. The combined experimental evidence, along with the aid of electronic structure calculations (density functional theory and time-dependent density functional theory performed at the M06/Def2-SVP/SDD level), illustrates that the CNAr ligand is actively engaged in manipulating the excited-state decay in three of these molecules (2-4), wherein the triplet metal-to-ligand charge-transfer (3MLCT) state along with two distinct triplet ligand-centered (3LC) excited-state configurations (phen and CNAr) conspire to produce the resultant photophysical properties. Because the π conjugation within the CNAr ligand was extended, an interesting shift in the dominant photophysical processes was observed. When the CNAr conjugation length is short, as in 1, the phenanthroline 3LC state dominates, resulting in a configurationally mixed triplet excited state of both LC and MLCT character. With more extended π conjugation in the CNAr subunit (2-4), the initially generated 3LC(phen)/3MLCT excited state ultimately migrates to the CNAr 3LC state on the order of tens of picoseconds. Molecules 3 and 4 in this series also feature unique examples of inorganic excimer formation, as evidenced by dynamic self-quenching in the corresponding PL intensity decays accompanied by the observation of a short-lived low-energy emission feature.

Photoinduced Intercomponent Processes in Selectively Addressable Bichromophoric Dyads Made of Linearly Arranged Ru(II) Terpyridine and Expanded Pyridinium Components.

Three new linearly arranged bichromophoric systems 1-3 have been prepared, and their photophysical properties have been studied, taking also advantage of femtosecond pump-probe transient absorption spectroscopy. The three compounds contain the same chromophores, that is a Ru(II)-terpy-like species and a fused expanded bipyridinium (FEBP) unit, separated by three different, variously methylated biphenylene-type bridges. The chromophores have been selected to be selectively addressable, and excitation involving the Ru-based or the FEBP-based dyes results in different excited-state decays. Upon Ru-based excitation at 570 nm, oxidative photoinduced electron transfer (OPET) takes place in 1-3 from the 3MLCT state; however, the charge-separated species does not accumulate, indicating that the charge recombination rate constant exceeds the OPET rate constant. Upon excitation of the organic dye at 400 nm, the FEBP-based 1π-π* level is prepared, which undergoes a series of intercomponent decay events, including (i) electron-exchange energy transfer leading to the MLCT manifold (SS-EnT), which successively decays according to 570 nm excitation, and (ii) reductive photoinduced electron transfer (RPET), leading to the preparation of the charge-separated (CS) state. Reductive PET, involving the FEBP-based singlet state, is much faster than oxidative PET, involving the MLCT triplet state, essentially because of driving force reasons. The rate constant of CR is intermediate between the rate constants of OPET and RPET, and this makes 1-3 capable to selectively read the 400 nm excitation as an active input to prepare the CS state, whereas excitation at wavelengths longer than 480 nm is inefficient to accumulate the CS state. Moreover, intriguing differences between the rate constants of the various processes in 1-3 have been analyzed and interpreted according to the superexchange theory for electron transfer. This allowed us to uncover the role of the electron-transfer and hole-transfer superexchange pathways in promoting the various intercomponent photoinduced decay processes occurring in 1-3.

Oxygen quenching of the excited MLCT state of ruthenium (II) bipyridyl heteroleptic complexes and singlet oxygen thereby produced

Oxygen quenching of the excited MLCT state of ruthenium (II) bipyridyl heteroleptic complexes and singlet oxygen thereby produced

Oxygen quenching of the excited MLCT state of ruthenium (II) bipyridyl heteroleptic complexes and singlet oxygen thereby produced

Oxygen quenching of the excited MLCT state of ruthenium (II) bipyridyl heteroleptic complexes and singlet oxygen thereby produced

Light-activated ruthenium (II)-bicalutamide prodrugs for prostate cancer

Targeted delivery of clinically approved anticancer drug to tumor sites is an effective way to achieve enhanced drug efficacy as well as reduced side effects and toxicity. Here bicalutamide is caged by the Ru(II) center through the nitrile group, and three photoactive Ru(II) complexes were designed and synthesized. Docking study showed that the ruthenium(II) fragments can effectively block the binding of complexes 1–3 with AR (androgen receptor) owing to the large steric structures, thus bicalutamide in complexes 1–3 could not interact with AR-LBD (ligand binding domain). Once irradiation with blue light (465nm), complexes 1–3 can release bicalutamide and anticancer Ru(II) fragments, which possesses dual-action of AR binding and DNA interaction simultaneously. In vitro cytotoxicity study on these complexes further confirmed that complexes 1–3 exhibited considerable cytotoxicity upon irradiation with blue light. Significantly, complex 3 could be activated at 660nm, which greatly increases the scope of complex 3 to treat deeper within tissue. Theoretical calculations showed that the lowest singlet excitation energy of complex 3 is lower than those of complexes 1–2, which explains the experimental results well. Moreover, the 3MC (metal centered) states of these complexes are more stable than their 3MLCT (metal to ligand charge transfer) states, indicating that the photoactive processes of these complexes are likely to result in ligand dissociation.

Unraveling the luminescence of new heteroleptic Ir(III) cyclometalated series

Three molecular engineered [Ir(N^C)2(CF3pic)] complexes, where N^C are Fppy = 2-(2,4-difluorophenyl)pyridine, ppy = 2-phenylpyridine or Meppy = 2-(p-tolyl)pyridine, and CF3pic = 3-(trifluoromethyl)pyridine-2-carboxylate, are reported to elucidate their photophysical characteristics and emission profiles to emphasize rigidochromism. Their emission in fluid media is ascribed to a lowest-lying 3MLCT (metal-to-ligand charge transfer) excited state with emission quantum yields (ϕ) at room temperature of 0.13 for [Ir(Fppy)2(CF3pic)] and ϕ < 0.01 for other compounds. In poly(methyl methacrylate) (PMMA) and at 77 K, a medium effect is observed through prominent spectral changes assigned to destabilization of the 3MLCT state and emission originated from the 3LC (ligand center) state. Emission energies in different media are rationalized through energy diagrams and rigidity-dependence of the emitted color is thoroughly depicted through CIE coordinates.

Stimuli-Responsive Near-Infrared Emissive Os(II)-Terpyridine Complexes with a Sense of Logic.

Two bis-tridentate Os(II) compounds based on a heteroditopic terpyridine–bipyridine-type ligand were synthesized, and their photophysical properties were thoroughly studied. The compounds exhibit strong spin-allowed 1MLCT bands in the visible domain (489–521 nm) as well as weak 1GS to 3MLCT bands within the 668–815 nm domain. The compounds display strong luminescence from the 3MLCT state in the near-infrared domain (728–780 nm) at room temperature having lifetimes in the range of 20.0–171.0 ns. After coordination of [Os(tpy-PhCH3/H2pbbzim)2]2+ unit to the terpyridine site of tpy-Hbzim-dipy, the complexes offer vacant pyridine–imidazole motifs for interacting with cationic and anionic guests. Consequently, photophysical properties of the compounds were tuned to a great extent upon interaction with selected cations, anions, pH, as well as protons. Anion-induced alteration of the ground- and excited-state properties of the compound lead to recognition of specific anions in solution. Significant change in the optical spectral behaviors as well as switching of emission spectral properties of the compounds was done in the NIR region upon treating with anions, cations, protons, and solvents (dichloromethane, acetonitrile, methanol, dimethylsulfoxide, and water). Moreover, the optical outputs in response to external stimuli were used to demonstrate binary functions of two-input IMPLICATION, NOR, and XNOR logic gates.

Effect of Molecular Conformation Restriction on the Photophysical Properties of N^N Platinum(II) Bis(ethynylnaphthalimide) Complexes Showing Close-Lying 3MLCT and 3LE Excited States.

Using naphthalimide (NI), complexes (Pt-PhNI and Pt-PhMeNI) based on the N^N platinum(II) bis(phenylacetylide) coordination framework were prepared, in which there are two close-lying triplet states, i.e., the metal-to-ligand-charge-transfer (3MLCT) and the NI localized emissive state (3LE). Pt-PhNI has better electronic communication between the Pt coordination center and the NI moiety, whereas in Pt-PhMeNI, they are more isolated by orthogonal geometry. For Pt-PhMeNI, the S0 → 1MLCT and S0 → 1LE absorption bands are separated by 5655 cm-1, while they are more overlapped in Pt-PhNI. The 3MLCT → S0 and 3LE → S0 dual phosphorescence emissions were observed for both Pt-PhNI (in toluene) and Pt-PhMeNI (in benzonitrile). The molecular conformation tunes the 3MLCT/3LE state population ratio, and the orthogonal geometry makes the 3LE state in Pt-PhMeNI basically a dark state (in toluene). Switching of the relative energy levels of the 3MLCT/3LE states by variation of the solvent polarity and temperature was achieved. For Pt-PhMeNI, the energy level of 3MLCT state is higher in a polar solvent; thus, the 3MLCT emission decreases, while the phosphorescence lifetime is prolonged from 9.5 μs (in toluene) to 58 μs (in benzonitrile) because of the different equilibria with the nonemissive 3LE state. Conversely, increasing the temperature enhances the upward transition from the nonemissive 3LE state to the emissive 3MLCT state; as such, the phosphorescence of Pt-PhMeNI was intensified at higher temperature (which is unusual), and the phosphorescence lifetime decreased from 58 μs (298 K) to ca. 5 μs (348 K). The ultrafast intersystem crossing (ca. 0.5 ps) and intramolecular triplet-triplet energy transfer (3-11 ps) were studied by femtosecond transient absorption spectroscopy. These results are useful for an in-depth understanding of the photophysics of multichromophore transition-metal complexes and for the design of external stimuli-responsive sensing materials, for instance, temperature or microenvironment sensing materials.

Heteronuclear d-d and d-f Ru(ii)/M complexes [M = Gd(iii), Yb(iii), Nd(iii), Zn(ii) or Mn(ii)] of ligands combining phenanthroline and aminocarboxylate binding sites: combined relaxivity, cell imaging and photophysical studies.

A ligand skeleton combining a 1,10-phenanthroline (phen) binding site and one or two heptadentate N3O4 aminocarboxylate binding sites, connected via alkyne spacers to the phen C3 or C3/C8 positions, has been used to prepare a range of heteronuclear Ru·M and Ru·M2 complexes which have been evaluated for their cell imaging, relaxivity, and photophysical properties. In all cases the phen unit is bound to a {Ru(bipy)2}2+ unit to give a phosphorescent {Ru(bipy)2(phen)}2+ luminophore, and the pendant aminocarboxylate sites are occupied by a secondary metal ion M which is either a lanthanide [Gd(iii), Nd(iii), Yb(iii)] or another d-block ion [Zn(ii), Mn(ii)]. When M = Gd(iii) or Mn(ii) these ions provide the complexes with a high relaxivity for water; in the case of Ru·Gd and Ru·Gd2 the combination of high water relaxivity and 3MLCT phosphorescence from the Ru(ii) unit provides the possibility of two different types of imaging modality in a single molecular probe. In the case of Ru·Mn and Ru·Mn2 the Ru(ii)-based phosphorescence is substantially reduced compared to the control complexes Ru·Zn and Ru·Zn2 due to the quenching effect of the Mn(ii) centres. Ultrafast transient absorption spectroscopy studies on Ru·Mn (and Ru·Zn as a non-quenched control) reveal the occurrence of fast (<1 ns) PET in Ru·Mn, from the Mn(ii) ion to the Ru(ii)-based 3MLCT state, i.e. MnII-(phen˙-)-RuIII → MnIII-(phen˙-)-RuII; the resulting MnIII-(phen˙-) state decays with τ ≈ 5 ns and is non-luminescent. This occurs in conformers when an ET pathway is facilitated by a planar, conjugated bridging ligand conformation connecting the two units across the alkyne bridge but does not occur in conformers where the two units are electronically decoupled by a twisted conformation of the bridging ligand. Computational studies (DFT) on Ru·Mn confirmed both the occurrence of the PET quenching pathway and its dependence on molecular conformation. In the complexes Ru·Ln and Ru·Ln2 (Ln = Nd, Yb), sensitised near-infrared luminescence from Nd(iii) or Yb(iii) is observed following photoinduced energy-transfer from the Ru(ii) core, with Ru → Nd energy-transfer being faster than Ru → Yb energy-transfer due to the higher density of energy-accepting states on Nd(iii).