Low-energy Electronic Transitions Research Articles

Turn-On Fluorescence Probe for Cancer-Related γ-Glutamyltranspeptidase Detection.

The design and development of fluorescent materials for detecting cancer-related enzymes are crucial for cancer diagnosis and treatment. Herein, we present a substituted rhodamine derivative for the chromogenic and fluorogenic detection of the cancer-relevant enzyme γ-glutamyltranspeptidase (GGT). Initially, the probe is non-chromic and non-emissive due to its spirolactam form, which hinders extensive electronic delocalization over broader pathway. However, selective enzymatic cleavage of the side-coupled group triggers spirolactam ring opening, resulting in electronic flow across the rhodamine skeleton, and reduces the band gap for low-energy electronic transitions. This transformation turns the reaction mixture from colorless to intense pink, with prominent UV and fluorescence bands. The sensor's selectivity was tested against various human enzymes, including urease, alkaline phosphatase, acetylcholinesterase, tyrosinase, and cyclooxygenase, and showed no response. Absorption and fluorescence titration analyses of the probe upon incremental addition of GGT into the probe solution revealed a consistent increase in both absorption and emission spectra, along with intensified pink coloration. The cellular toxicity of the receptor was evaluated using the MTT assay, and bioimaging analysis was performed on BHK-21 cells, which produced bright red fluorescence, demonstrating the probe's excellent cell penetration and digestion capabilities for intracellular analytical detection. Molecular docking results supported the fact that probe-4 made stable interactions with the GGT active site residues.

Hexaguanidino-Triptycenes and Triphenylenes: Electronic Coupling in Molecules Containing Three Redox-Active o-Diguanidinobenzene Units Connected either Directly or Interacting Through Homoconjugation.

Novel redox-active hexaguanidine molecules with multiple redox states were synthesized by connecting three o-diguanidinobenzene units. In 2,3,6,7,14,15-hexaguanidino-triptycenes, the three redox-active o-diguanidinobenzene units are connected through C-C bonds to the sp3 -hybridized bridgehead C atoms, and in 2,3,6,7,10,11-hexaguanidino-triphenylenes they are directly connected. The connectivity difference leads to different electronic coupling between the three redox-active o-diguanidinobenzene units, with homoconjugation being present in the triptycene, but not in the triphenylene compounds. Motivated by the appearance of an intense low-energy electronic transition, we especially analysed the effect of homoconjugation on the electronic structure and charge delocalization in the dicationic redox state of the triptycene derivatives. Then, several trinuclear high-spin cobalt (and copper) complexes were synthesized with the triphenylene and triptycene ligands, and the magnetic coupling and redox properties analysed. By choice of the coligands (hexafluoroacetylacetonate, trifluoroacetylacetonate and acetylacetonate), oxidation could be switched between metal- and ligand-centered redox events, leading to drastic changes in the magnetic or optical properties, especially as a consequence of homoconjugation in the triptycene derivatives.

A comparative analysis of UV–vis transitions in hetaryl and ferrocenyl thioketones

Electronic transitions in a series of symmetrical and nonsymmetrical hetaryl- and/or ferrocenyl-functionalized thioketones have been studied using quantum chemistry methods. An in-depth theoretical characterization was carried out for low-energy electronic transitions. The effects of hetaryl and ferrocenyl groups on the energy of these transitions were recognized and elucidated in terms of atomic and molecular orbital contributions involved in the transitions. A comparison was drawn between the low-energy transitions in the thioketones and in their carbonyl counterparts. The effect of solvents on the position of UV–vis absorption bands, in particular, on those originating in the low-energy transitions, is discussed. The theoretical calculations indicate that the introduction of ferrocenyl group into the hetaryl-functionalized thioketones changes the character of their first two electronic transitions from n → π* and π → π* into dominant d → π*. The most intense band of all studied thioketones appears in the near-UV region and undergoes a redshift upon solvation.

Mixed Valence of Bismuth in Hexagonal Chalcohalide Nanocrystals

We report the colloidal synthesis of bismuth chalcohalide nanocrystals, which adopt a hexagonal phase that we describe with the Bi13S18X2 (in which X = Br and I) structure. Such a model structure displays columns of Bi atoms that form dimers of subvalent Bi (formally Bi24+), which we here ascribe to Peierls-type distortions. We suggest that the Bi24+ dimers are at the origin of the anomalously low band gap of this material, with the lowest energy electronic transition showing analogies with an intervalence charge transfer. Our synthetic approach and insights into the structural and electronic features of the hexagonal bismuth chalcohalides are fundamental to sustain the rapidly increasing use of this class of (nano)materials for diverse applications, such as photocatalysis and thermoelectrics.

On the non-bonding valence band and the electronic properties of poly(triazine imide), a graphitic carbon nitride.

Graphitic carbon nitrides are covalently-bonded, layered, and crystalline semiconductors with high thermal and oxidative stability. These properties make graphitic carbon nitrides potentially useful in overcoming the limitations of 0D molecular and 1D polymer semiconductors. In this contribution, we study structural, vibrational, electronic and transport properties of nano-crystals of poly(triazine-imide) (PTI) derivatives with intercalated Li- and Br-ions and without intercalates. Intercalation-free poly(triazine-imide) (PTI-IF) is corrugated or AB stacked and partially exfoliated. We find that the lowest energy electronic transition in PTI is forbidden due to a non-bonding uppermost valence band and that its electroluminescence from the π-π* transition is quenched which severely limits their use as emission layer in electroluminescent devices. THz conductivity in nano-crystalline PTI is up to eight orders of magnitude higher than the macroscopic conductivity of PTI films. We find that the charge carrier density of PTI nano-crystals is among the highest of all known intrinsic semiconductors, however, macroscopic charge transport in films of PTI is limited by disorder at crystal-crystal interfaces. Future device applications of PTI will benefit most from single crystal devices that make use of electron transport in the lowest, π-like conduction band.

Electronic spectroscopy of homo- and heterometallic binuclear coinage metal phosphine complexes in isolation.

Binuclear coinage metal phosphine complexes are examined under ion trap isolation in order to elucidate their noncovalent binding, structural properties and intrinsic electronic spectra. Our survey shows an intriguing order of electronic transitions obtained by in situ synthesis and mass-spectrometrically supported UV photodissociation spectroscopy on a series of six isolated homo- and heterobinuclear complexes of type [MM'(dcpm)2]2+ (M, M' = CuI, AgI, AuI; dcpm = bis(dicyclohexyl-phosphino)methane). This approach provides the unique opportunity to study all possible coinage metal interactions within a fixed ligand framework. A successive blue-shift (33 700-38 500 cm-1; 297-260 nm) of the lowest-energy bright electronic transition energy in gas phase was observed in the order of Cu2 < CuAu < CuAg < Au2 < AgAu < Ag2. This order was reproduced by quantum chemical calculations using a scalar-relativistic GW-Bethe-Salpeter-equation (GW-BSE) approach. Theory ascribes the electronic bands of all complexes to metal-centered 1MC(dσ*-pσ) transitions revealing a strengthening of metal-metal' (M-M') binding upon excitation, in agreement to mass spetrometric results. A test of the correlation of transition energies with M-M' distance by quantum chemical calculations of single point energies as a function of intermetallic distance indicates qualitative agreement with experimental results. However, the experimentally observed high sensitivity of spectroscopic shifts towards metal composition cannot be accounted for solely by M-M' distance variation. The differences in electronic transitions are qualitatively rationalized by the varying (n + 1)s (n = 3, 4, 5) orbital contributions (increase from Cu2via CuAu/CuAg to Au2/AgAu/Ag2) within the nd(n + 1)s/p-hybridization for the ground electronic state of the different complexes, whereas the excited state (of (n + 1)p orbital character) shows significantly less variation in energy. In particular, the observed spectroscopic and mass spectrometric sequence for the Ag/Au complexes is traced back to the interplay of Pauli repulsion and variation in metal-ligand bond strength within the orbital hybridization model.

Synthesis, structure and photoluminescence of Cu(I) complexes containing new functionalized 1,2,3-triazole ligands.

The reaction of a triazole ligand, 2-(1H-1,2,3-triazol-4-yl)pyridine (L1), with 2-bromopyridine afforded three new ligands, 2,2'-(1H-1,2,3-triazole-1,4-diyl)dipyridine (L2), 2,2'-(2H-1,2,3-triazole-2,4-diyl)dipyridine (L3) and 2,2'-(1H-1,2,3-triazole-1,5-diyl)dipyridine (L4). A series of luminescent mononuclear copper(I) complexes of these ligands [Cu(Ln)(P^P)](ClO4) [n = 1, P^P = (PPh3)2 (1); n = 1, P^P = POP (2); n = 2, P^P = (PPh3)2 (3); n = 2, P^P = POP (4); n = 3, P^P = (PPh3)2 (5); n = 3, P^P = POP (6); n = 4, P^P = (PPh3)2 (9); n = 4, P^P = POP (10)] have been obtained from the reaction of Ln with [Cu(MeCN)4]ClO4 in the presence of PPh3 and POP. L3 was also found to form dinuclear compounds [Cu2(L3)(PPh3)4](ClO4)2 (7) and [Cu2(L3)(POP)2](ClO4)2 (8). All of the Cu(I) compounds have been characterized by IR, UV/vis, CV, 1H NMR, and 31P{1H} NMR. The molecular structures of 1-3, 5, and 7 have been further determined by X-ray crystallography. In CH2Cl2 solutions, these Cu(I) complexes exhibit tunable green to orange emissions (563-621 nm) upon excitation at λex = 380 nm. In the solid state, these complexes show intense emissions and it is interesting to note that 1 and 3 are blue-light emitters. Density functional theory (DFT) calculations revealed that the lowest energy electronic transition associated with these complexes predominantly originates from metal-to-ligand charge transfer transitions (MLCT).

Absorption spectra of calix[3]pyrrole analogs as probes for contracted macrocycles

Calix[3]pyrrole and its furan derivatives exhibited bathochromically shifted lowest-energy electronic transition bands in their absorption spectra compared with their calix[4]- and calix[6]-pyrrole analogues, despite the repeating units being the same. We also observed fluorescence emission for calix[3]-type macrocycles. The Stokes shift of the furan/pyrrole hybrid macrocycles, calix[2]furan[1]-pyrrole, and calix[1]furan[2]pyrrole, substantially varied depending on the solvent polarity. Non-covalent interaction (NCI) analyses indicated enhanced interactions between neighboring aromatic rings in the calix[3]pyrrole macrocycle, whereas such interactions were weak in calix[4]pyrrole, in which the interchromophore distance is remarkably longer than in calix[3]pyrrole. Theoretical analyses indicated that the red-shifted, lowest-energy bands of calix[3]pyrrole correspond to HOMO–LUMO transitions, the energy gap of which was narrow compared with calix[4]pyrroles. The characteristic absorption bands for calix[3]pyrrole and its related macrocycles are useful as probes for distinguishing such macrocycles from higher calix[[Formula: see text]]pyrrole ([Formula: see text] 4) analogues that exhibit almost identical absorption spectra.

Synthesis, structures, and photophysical properties of two Cu(I) complexes supported by N-heterocyclic carbene and phosphine ligands

Abstract Two new cationic four-coordinate Cu(I) complexes supported by different chelating N-heterocyclic carbene ligands and the diphosphine ligand bis[2-(diphenylphosphino)phenyl]ether (POP) have been synthesized. The chemical structures of both complexes have been characterized by 1H NMR, 13C NMR, 31P NMR, and mass spectroscopy, and the crystal structure of one complex has been determined by single-crystal X-ray diffraction. Results of theoretical calculations indicate that the lowest energy electronic transitions of these complexes are mainly the metal-to-ligand charge transfer and ligand-to-ligand charge transfer transitions. The complexes in solid state show intense emissions with high photoluminescence quantum yields. The photophysical behavior at 298 and 77K shows that emissions of these complexes at room temperature are thermally activated delayed fluorescence mixed with phosphorescence.

Nitrogen-Embedded Multi-Resonance Heteroaromatics with Prolonged Homogeneous Hexatomic Rings.

Nitrogen-containing polycyclic heteroaromatics have exhibited fascinating multi-resonance (MR) characteristics for efficient narrowband emission, but strategies to bathochromic shift their emissions while maintaining the narrow bandwidths remain exclusive. Here, homogeneous hexatomic rings are introduced into nitrogen-embedded MR skeletons to prolong the π-conjugation length for low-energy electronic transitions while retaining the non-bonding character of the remaining parts. The proof-of-the-concept emitters exhibit near unity photoluminescence quantum yields with peaks at 598 nm and 620 nm and small full-width-at-half-maximums of 28 nm and 31 nm, respectively. Optimal organic light-emitting diodes exhibit a high external quantum efficiency of 18.2 %, negligible efficiency roll-off, and ultra-long lifetime with negligible degradation at an initial luminance of 10 000 cd m-2 after 94 hours.

General Design Rules for Bimetallic Platinum(II) Complexes.

A series of platinum(II) bimetallic complexes were studied to investigate the effects of ligands on both the geometric and electronic structure. Modulating the Pt-Pt distance through the bridging ligand architecture was found to dictate the nature of the lowest energy electronic transitions, localized in one-half of the molecule or delocalized across the entire molecule. By reducing the separation between the platinum atoms, the lowest energy electronic transitions will be dominated by the metal-metal-to-ligand charge transfer transition. Conversely, by increasing the distance between the platinum atoms, the lowest electronic transition will be largely localized metal-to-ligand charge transfer or ligand centered in nature. Additionally, the cyclometalating ligands were observed to have a noticeable stabilizing effect on the triplet excited states as the conjugation increased, arising from geometric reorientation and increased electron delocalization of the ligands. Such stabilization of the triplet state energy has been shown to alter the excited state potential energy landscape as well as the excited state trajectory.

In Situ Spectroelectrochemical-Conductance Measurements as an Efficient Tool for the Evaluation of Charge Trapping in Conducting Polymers.

In situ UV-vis-NIR spectroelectrochemistry has been intensively used to evaluate the electronic transitions during the charging/discharging process of π-conjugated polymers. However, the type of charge carrier and the mechanisms of their transport, remains still a point of discussion. Herein, the coupling between UV-vis-NIR spectroscopy and in situ electrochemical-conductance measurements is proposed to compare the doping process of three different thiophene-based conducting polymers. The simultaneous monitoring of electrical and absorption properties, associated with low energy electronic transitions characteristic for polarons and bipolarons, was achieved. In addition, this method allows evaluating the reversible charge trapping mechanism of poly-3,4-o-xylendioxythiophene (PXDOT), caused by the formation of σ-dimers, making it a very useful tool to determine relevant physicochemical properties of conductive materials.

Relief of excited-state antiaromaticity enables the smallest red emitter

It is commonly accepted that a large π-conjugated system is necessary to realize low-energy electronic transitions. Contrary to this prevailing notion, we present a new class of light-emitters utilizing a simple benzene core. Among different isomeric forms of diacetylphenylenediamine (DAPA), o- and p-DAPA are fluorescent, whereas m-DAPA is not. Remarkably, p-DAPA is the lightest (FW = 192) molecule displaying red emission. A systematic modification of the DAPA system allows the construction of a library of emitters covering the entire visible color spectrum. Theoretical analysis shows that their large Stokes shifts originate from the relief of excited-state antiaromaticity, rather than the typically assumed intramolecular charge transfer or proton transfer. A delicate interplay of the excited-state antiaromaticity and hydrogen bonding defines the photophysics of this new class of single benzene fluorophores. The formulated molecular design rules suggest that an extended π-conjugation is no longer a prerequisite for a long-wavelength light emission.

Perylene diimide/MXene-modified graphitic pencil electrode-based electrochemical sensor for dopamine detection.

The synthesis of novel architecture comprising perylene diimide (PDI)-MXene (Ti3C2TX)-integrated graphitic pencil electrode for electrochemical detection of dopamine (DA)is reported. The good electron passage between PDI-MXene resulted in an unprecedented nano-adduct bearing enhanced electrocatalytic activity with low-energy electronic transitions. The anionic groups of PDI corroborated enhanced active surface area for selective binding and robust oxidation of DA, thereby decreasing the applied potential. Meanwhile, the MXene layers acted as functional conducive support for PDI absorption via strong H-bonding. The considerable conductivity of MXene enhanced electron transportation thus increasing the sensitivity of sensing interface. Theinclusively engineered nano-adduct resulted in robust DA oxidation with ultra-sensitivity (38.1 μAμM-1cm-2), andlow detection limit (240 nM) at very low oxidation potential (-0.135 V). Moreover, it selectively signaled DA in the presence of physiological interferents with wide linearity (100-1000 μM). The developed transducing interface performed well in human serum samples with RSD (0.1 to 0.4%) and recovery (98.6 to 100.2%) corroborating the viability of the practical implementation of this integrated system. Graphical abstract Schematic illustration of the oxidative process involved on constructed sensing interface for the development of a non-enzymatic dopamine sensor.

Near-Infrared Luminescence in Trinuclear Mixed-Metal Chalcogenolate Complexes of the Types [M2Ti(EPh)6(PPh3)2] (M = Cu, Ag; E = S, Se) and [Na(thf)3]2[Ti(SPh)6

The optical properties of four new trinuclear chalcogenolato bridged metal complexes [Ag2Ti(SPh)6(PPh3)2], [Na(thf)3]2[Ti(SPh)6], [Cu2Ti(SePh)6(PPh3)2], and [Ag2Ti(SePh)6(PPh3)2] have been investigated by absorption and photoluminescence spectroscopy as well as time-dependent density functional theory (TDDFT) calculations and compared to the results published recently for [Cu2Ti(SPh)6(PPh3)2]. All of these compounds are distinguished by efficient near-infrared luminescence at ∼880-1200 nm in the solid state at low temperatures, which remains quite intense for the copper-titanium complexes at ambient temperature with PL quantum yields of 9.5 and 4.8% at λPL = 1090 and 1240 nm for [Cu2Ti(EPh)6(PPh3)2], E = S, Se, respectively. According to the calculations, a peculiar feature of the lowest-energy electronic transitions in these complexes is their high localization on the metal and chalcogen atoms, with negligible contributions of the "external" ligand groups. Correspondingly, the type of atoms in the M2TiE6 (M = Cu, Ag, Na) core structure determines optical properties such as the absorption and emission wavelengths and PL lifetime.

Probing the Charge Transfer in a Frustrated Lewis Pair by Resonance Raman Spectroscopy and DFT Calculations.

A classical Lewis adduct derives from a covalent bond between a Lewis acid and a base. When the adduct formation is precluded by means of steric hindrance the association of the respective acid-base molecular system is defined as a frustrated Lewis pair (FLP). In this work, the archetypal FLP Mes3 P/B(C6 F5 )3 was characterized for the first time by resonance Raman spectroscopy, and the results were supported by density functional theory (DFT) calculations. The charge transfer nature of the lowest energy electronic transition, from phosphine to borane, was confirmed by the selective enhancement of the Raman bands associated to the FLP chromophore at resonance condition. Herein, we demonstrate the use of resonance Raman spectroscopy as a distinguished technique to probe the weak interaction involved in FLP chemistry.

On the Ruhemann’s Purple electronic spectrum: the role of torsion angle and coordination with Zn(II)

The Ruhemann's Purple (RP) is a chromophore formed from ninhydrin reaction with amines mainly applied to develop latent fingerprints in forensic science. Further enhancement of RP photoluminescence is achieved thought post-treatment with transition metal salt (commonly ZnCl2 alcohol solution), due to the coordination of RP with the metal ion. The literature attributes this improvement to the RP planarity increase in the complex, suggesting this characteristic as important to the post-treatment success. In the present work, the experimentally reported ZnRP complexes and the isolated RP ligand were investigated at the ωB97XD/6-311++G(d,p)/LanL2DZ/IEFPCM(MeOH) level, and their geometrical parameters, complexation energies, and spectroscopic properties (harmonic vibrations and electronic spectrum) were evaluated and agree with the experimental data. The systematic variation of the RP planarity (tilt angle) showed that the lowest energy electronic transition is quite sensitive to RP of this torsion angle. However, the RP planarity increase corresponds to approximately 30% of the total band shift achieved in the complex formation. The results reinforce the importance of the metal ion in the photoluminesce property changing and draw attention to improvements on transition metal complexes design in the post-treatment of developed latent fingermarks.

Organoimido functionalized trinuclear gold(I) clusters with fluorescent chromophore

The post-functionalization of gold nanoclusters with organic molecules into organic–inorganic hybrid functional materials is an efficient approach to develop multifunctional materials. By introducing 1-pyrenamine and 3-aminofluoranthene into [O(AuPPh3)3][BF4] with a covalent bond, two novel organoimido functionalized trinuclear gold nanoclusters [C16H9N(AuPPh3)3][BF4] (Au3–P) and [C6H4–C10H5N(AuPPh3)3][BF4] (Au3–F) have been successfully obtained. Their structures have been determined by electrospray ionization mass spectroscopy (ESI–MS) and single-crystal X-ray diffraction (SC-XRD), and the photoluminescence properties have been investigated from both experimental and theoretical aspects. It is found that the lowest-energy electronic transitions in the ultraviolet–visible (UV–Vis) absorption spectra of Au3–P (403 nm) and Au3–F (425 nm) exhibit a slight bathochromic shift compared to the corresponding transitions in the spectra of 1-pyrenamine and 3-aminofluoranthene, respectively. In addition, the dichloromethane solutions of Au3–P and Au3–F complexes clearly display blue and yellowish-green fluorescence, respectively. These results will help to design and prepare organic–inorganic nanocluster hybrid luminescent materials for potential applications in (bio)sensors, bioimaging and optoelectronic devices.

Non-linear optical behavior of benzothiazole based chromophores: Second harmonic generation

The linear as well as second-order non-linear optical behavior of benzothiazole based chromophores and their corresponding boron (III) chelated derivatives has been discerned. The participating high energy (HE) and low energy (LE) electronic transitions of these compounds and the corresponding orbitals have been characterized on the basis of time dependent density functional theory (TD-DFT) calculations. The experimental electronic spectral data as well as electrochemical data correlated well with the calculated band gaps and the natural bond orbital (NBO) values, respectively. The experimentally determined second-order polarizability, β, values show structure dependence and good correlation with the electronic absorption data. The boron (III) chelated chromophores exhibit higher values of βHRS compared to their non-chelated counterparts as expected from the π-electron density delocalization in the chromophores, although the trend in β values corrected for resonance enhancement changed. Significant thermal stability of these chromophores (up to 300 °C) is an additional attribute that purports these chromophores as promising candidates for electro-optics and related applications.

Ultralow-Transition-Energy Organic Complex on Graphene for High-Performance Shortwave Infrared Photodetection.

Room-temperature, high-sensitivity, and broadband photodetection up to the shortwave infrared (SWIR) region is extremely significant for a wide variety of optoelectronic applications, including contamination identification, thermal imaging, night vision, agricultural inspection, and atmospheric remote sensing. Small-bandgap semiconductor-based SWIR photodetectors generally require deep cooling to suppress thermally generated charge carriers to achieve increased sensitivity. Meanwhile, the photogating effect can provide an alternative way to achieve superior photosensitivity without the need for cooling. The optical photogating effect originates from charge trapping of photoinduced carriers at defects or interfaces, resulting in an extremely high photogain (106 or higher). Here, a highly sensitive SWIR hybrid photodetector, fabricated by integrating an organic charge transfer complex on a graphene transistor, is reported. The organic charge transfer complex (tetrathiafulvalene-chloranil) has an exceptional low-energy intermolecular electronic transition down to 0.5 eV, with the aim of achieving efficient SWIR absorption for wavelengths greater than 2 µm. The photogating effect at the organic complex and graphene interface enables an extremely high photogain and a high detectivity of ≈1013 Jones, along with a response time of 8 ms, at room temperature for a wavelength of 2 µm.