Chapter Eight - Material Dependence of Water Interactions with Metal Oxide Nanoparticles: TiO2, SiO2, GeO2, and SnO2

Cyclometalated diruthenium complexes 1(PF6)2-5(PF6)2 bridged by 1,3,6,8-tetra(pyrid-2-yl)-pyrene have been prepared, with the terminal ligand bis(N-methylbenzimidazolyl)pyridine (1(PF6)2), 4'-di-(p-methoxyphenyl)amino-2,2':6',2″-terpyridine (2(PF6)2), 4'-p-methoxyphenyl-2,2':6',2″-terpyridine (3(PF6)2), 2,2':6',2″-terpyridine (4(PF6)2), and trimethyl-4,4',4″-tricarboxylate-2,2':6',2″-terpyridine (5(PF6)2). The single-crystal X-ray structure of 4(PF6)2 is presented. These complexes show two stepwise anodic redox pairs, and the potentials progressively increase from 1(PF6)2 to 5(PF6)2. Complexes 1(PF6)2-4(PF6)2 have comparable electrochemical potential splitting of 200-210 mV, while complex 5(PF6)2 has a splitting of 170 mV. Upon one-electron oxidation by chemical oxidation or electrolysis, the resulting mixed-valent complexes 1(3+)-5(3+) display broad and intense absorptions between 1000 and 3000 nm. Complexes 1(3+) and 2(3+) show the presence of a higher-energy shoulder band in addition to the main near-infrared absorption band. This shoulder band is less distinguished for 3(3+)-5(3+). Three-state theory has been used to explain this difference. The one-electron oxidized forms, 1(3+)-5(3+), exhibit rhombic EPR signals at 77 K with the isotropic g values in the range of 2.18-2.24. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations have been performed on 1(2+)-5(2+) to characterize their electronic structures and rationalize the absorption spectra in a wide energy range. DFT computations on 1(3+)-5(3+) show that both ruthenium ions and the bridging ligand have comparable spin densities. TDDFT computations on 1(3+) and 4(3+) have been performed to complement the experimental results.

Pseudopotentials (PP) are extensively used in electronic structure calculations, particularly for molecules containing heavy elements. Parameters in PPs are mainly determined from abinitio results, and errors of such PPs in density functional theory (DFT) calculations have been studied previously. However, PP errors on results with spin-orbit coupling and those in time-dependent DFT (TDDFT) calculations have not been reported previously. In this work, we investigate the error of the small-core energy-consistent Stuttgart/Koln pseudopotentials in DFT and TDDFT calculations with and without spin-orbit coupling. Ground state bond lengths, harmonic frequencies, dissociation energies, and vertical excitation energies for a series of closed-shell diatomic heavy and superheavy p-block molecules are calculated using several popular exchange-correlation functionals. PP errors are estimated by comparing with results using the all-electron Dirac-Coulomb (-Gaunt) Hamiltonian. Our results show that the difference between ground state properties and most excitation energies in scalar-relativistic calculations with the PP and those of all-electron calculations is quite small. This difference becomes somewhat larger when spin-orbit coupling (SOC) is present, especially for properties that are affected by SOC to some extent. In addition, the errors of the PPs are insensitive to the employed exchange-correlation functionals in most cases. Our results indicate that reasonable DFT and TDDFT results can be obtained using the small-core energy-consistent Stuttgart/Koln pseudopotentials for heavy and super-heavy p-block molecules.

The conventional approximate exchange-correlation functionals and kernels can lead to a large error in time-dependent density functional theory (TDDFT) calculations in certain cases, such as in the descriptions of charge-transfer excited states, Rydberg states, and double excitations, which can be remedied to some degree with the recently developed range-separated exchange-correlation functionals. How do these range-separated functionals perform in the TDDFT calculations? In this work, we explored the S0(A′) → T1(A′) and S0(A′) → S1(A′) transition energies of C2H4 and other molecules by TDDFT methods and ▵SCF calculations in density functional theory (DFT), with several regular and range-separated exchange-correlation functionals. We have found the following: (1) for the S0 → S1 transition, both range- and non-range-separated exchange-correlation functionals work well and consistently in the TDDFT calculations; (2) for the S0 → T1 transition, the used range-separated exchange-correlation functionals work on average worse than the non-separated ones in the TDDFT calculations; in the ▵SCF DFT calculations, however, both kinds of functionals achieve a similar performance. Because of the common approximations used in DFT and TDDFT, our present computational results suggest that the adiabatic approximation error in the range-separated exchange-correlation functionals is much larger than that in the non-range-separated ones for the S0 → T1 transition, and the adiabatic approximation error for the S0 → T1 transition – a spin-flip process – is larger than that for the S0 → S1 transition. These findings will be useful for designing better exchange-correlation functionals and kernels that will work well not only for excited singlet states, but also for excited triplet states. Furthermore, this study will provide insights into the drawbacks of the present approximate exchange-correlation functionals and kernels used in TDDFT calculations.

o-Imino-p-R'-benzosemiquinone anion radical (L(R')(IS)(˙-)) complexes of oxidovanadium(IV) of type [(L(1)(R-))(VO(2+))(L(R')(IS)(˙-))] (R = H, R' = H, 1; R = H, R' = -CMe(3), 2; R = -CMe(3), R' = H, 3 and R = -CMe(3), R' = -CMe(3), 4) incorporating the redox-innocent tridentate NNO-donor L(1)(R-) ligands (L(1)(R)H = 2,4-di-R-6-{(2-(pyridin-2-yl)hydrazono)methyl}phenol) were isolated and substantiated by elemental analyses, IR, mass, NMR and UV-vis spectra including the single crystal X-ray structure determinations. The V-O(phenolato) (cis to the V=O) lengths spanning 1.905(3)-1.9355(15) Å in 1-4 are consistent with the coordination to the [VO](2+) state. The V-O(IS) (trans to the V=O) lengths, 2.1505(17)-2.1869(15) Å, in 1-4 are longer due to the trans influence of the V=O bond. The V-N(IS) lengths, 1.906(3)-1.924(2) Å, in 1-4 are comparatively shorter due to the higher affinity of the paramagnetic [VO](2+) ion towards the L(R')(IS)(˙-) anion radicals. Density functional theory (DFT) calculations using B3LYP, B3PW91 and PBE1PBE functionals on 1 and 2 authenticated that the closed shell singlet (CSS) solutions (dianionic o-amido-p-R'-phenolates (L(R')(AP)(2-)) coordinated to VO(3+), Type I) of 1-4 are unstable with respect to the open shell singlet (OSS) perturbations. Broken symmetry, BS (1,1) M(s) = 0 (L(R')(IS)(˙-) coordinated to the VO(2+) ion, Type III) solutions of 1-4 are stable and reproduce the experimental bond parameters. Frozen glasses EPR spectra of [1-4](+) ions (e.g. g(||) = 1.948, g(⊥) = 1.978, A(||) = 184 (22 G), A(⊥) = 62(15 G) for [2](+)) and unrestricted DFT calculations on [1](+), [2](+), [1](-) and [2](-) ions using doublet spin state elucidated that the reversible anodic waves at [0.15-0.31] V of 1-4 complexes are due to the oxidation of L(R')(IS)(˙-) generating [(L(1)(R-))(VO(2+))(L(R')(IQ))]+ complexes (L(R')(IQ) = o-imino-p-R'-benzoquinone) coordinated to the [VO](2+) ion (Type V) while the irreversible cathodic waves at -[1.08-1.49] V are due to the formation of unstable [(L(1)(R-))(VO(2+))(L(R')(AP)(2-))](-) complexes (Type II). The second anodic waves at [0.76-0.89] V are assigned to a [VO](3+)-[VO](2+) couple affording diamagnetic [(L(1)(R-))(VO(3+))(L(R')(IQ))](2+), [1-4](2+) complexes (Type VI) which are identified by UV-vis spectra, DFT and time dependent (TD) DFT calculations. Spectro-electrochemical measurements and TD DFT calculations on 1 and 2 disclosed that lower energy electronic absorption bands of 1-4 are due to the LMCT and CSS-OSS perturbation which disappear in [1-4](+) ions. [1-4](+) absorb at 600-650 nm due to d-d transitions and MLCT which are absent in VO(3+) complexes, [1-4](2+).

Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, employing the B3LYP method and the LANL2DZ, 6-31G*(LANL2DZ for Tc), 6-31G*(cc-pVDZ-pp for Tc) and DGDZVP basis sets, have been performed to investigate the electronic structures and absorption spectra of the technetium-99m-labeled methylenediphosphonate ( 99m Tc-MDP) complex of the simplest diphosphonate ligand. The bonding situations and natural bond orbital compositions were studied by the Mulliken population analysis (MPA) and natural bond orbital (NBO) analysis. The results indicate that the σ and π contributions to the Tc-O bonds are strongly polarized towards the oxygen atoms and the ionic contribution to the Tc-O bonding is larger than the covalent contribution. The electronic transitions investigated by TDDFT calculations and molecular orbital analyses show that the origin of all absorption bands is ascribed to the ligand-to-metal charge transfer (LMCT) character. The solvent effect on the electronic structures and absorption spectra has also been studied by performing DFT and TDDFT calculations at the B3LYP/6-31G*(cc-pVDZ-pp for Tc) level with the integral equation formalism polarized continuum model (IEFPCM) in different media. It is found that the absorption spectra display blue shift in different extents with the increase of solvent polarity.

The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) < 3.5% and epsilon(SF) values close to unity (>0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes.

The evolution of the electronic structure and optical transition upon n-doping of poly(9,9-dioctylfluorene) (PFO) films is elucidated with photoelectron spectroscopy, optical absorption, density functional theory (DFT), and time-dependent DFT (TD-DFT) calculations. Optical absorption measurements extending into near infrared show two low-energy absorption features at low doping ratios and an additional peak at a higher energy of ∼2.2 eV that disappears with increasing doping ratios. A gap state (i.e., polaronic state) close to the Fermi level and a significantly destabilized highest valence band appear in the experimentally measured ultraviolet photoelectron spectra. These experimental results are interpreted by the TD-DFT calculations, which show that the lower energy peaks originate from the excitation from polaronic states to the conduction band, while the higher energy peak mainly originates from the destabilized valence band to conduction band transitions and only appears at low doping ratios (cred ≤ 50%, 0.5 potassium atom per fluorene monomer). The DFT calculations further indicate that polaron pairs rather than bipolarons are preferentially formed at high doping ratios. Comparing the results of doped glassy and β-phase films, we find that the ordered segments in the β-phase film disappear due to the dopant (potassium) insertion, resulting in a similar polaronic structure.

Quantum chemical investigations on the effect of dodecyloxy chromophore in 4-amino stilbene sensitizer for DSSCs

Dual-Responsive Thermally Activated Delayed Fluorescence of Spiropyran Derivatives

Novel thermally activated delayed fluorescence (TADF) host molecules for blue electrophosphorescence were developed by combining the electron donor acridine derivatives with the electron acceptor triphenylphosphine oxide unit in a single molecule based on density functional theory. We obtained the energies of the first excited singlet (S1) and triplet (T1) states of the TADF materials by performing procedures in accordance with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to the ground state using dependence on the charge transfer amounts for the optimal Hartree-Fock percentage in the exchange-correlation of TD-DFT. Using DFT and TD-DFT calculations, the significant separation between the HOMO and LUMO caused a small difference in energy (ΔEST) between the S1 and T1 states. The host molecules retained high triplet energy and showed great potential for use in blue phosphorescent organic light-emitting diodes. The results also showed that these molecules are promising TADF host materials because they demonstrate a low barrier to hole and electron injection, balanced charge transport for both holes and electrons, and small ΔEST.

Novel thermally-activated delayed fluorescence (TADF) host materials were designed for blue electrophosphorescence by combining electron donor acridine derivatives with the electron acceptor phenoxaphosphine (OPO) unit using the density functional theory. We obtained the energies of the first singlet (S1) and first triplet (T1) excited states of these TADF materials by performing density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations on the ground state using a dependence on charge transfer amounts for the optimal Hartree-Fock percentage in the exchange-correlation of the TD-DFT. Using DFT and TD-DFT calculations, the large separation between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) gives a small energy difference (ΔEST) between the S1 and T1 state. These host molecules could retain high triplet energy, and they showed great potential for blue phosphorescent organic light-emitting diodes (OLEDs). We demonstrated that these molecules are promising host materials with a lower barrier for hole and electron injection; these also provide balanced charge transport for both hole and electron and small ΔEST.

Herein we compare the electronic structures of the Co(I), Co(II), and Co(III) phthalocyanines, which were elucidated using UV-vis-NIR and magnetic circular dichroism (MCD) spectroscopy as well as density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The NIR triplet-multiplet bands in PcR4(2-)CoIIL2 (L = nil, Py, or nBuNH2; R = H or tert-Bu) complexes were studied by MCD spectroscopy for the first time and compared to those reported earlier by us in PcR4(2-)Cu (R = tert-Bu or SO3Na) compounds (J. Porphyrins Phthalocyanines 2025, 29, 110-122). In all cases, a Faraday MCD pseudo A-term was observed for this transition. DFT and TDDFT calculations successfully explained a systematic blue-shift in the metal-to-ligand charge-transfer (MLCT) and B1-band transitions going from [PcR4(2-)CoI]- to PcR4(2-)CoIIL2 to [PcR4(2-)CoIIIX2]- (X = CN- or Br-) complexes. Additionally, absorption bands observed in the 370-530 nm spectral envelope in [PcR4(2-)CoIIIX2]- complexes were assigned with a high level of confidence for the first time. This work provides the first combined systematic experimental and theoretical study that highlights similarities and differences in (magneto)optical spectroscopy of cobalt phthalocyanines spanning three oxidation states at the central metal ion.

S-Shaped Fused Azacorannulene Dimer: Structural and Redox Properties

A novel two-dimensional (2D), layered, helical supramolecular architecture constructed via cooperative hydrogen bond and halogen bonds was synthesized and characterized: [(BMBA)2(TPB)] n (1) [BMBA = 3-bromo-2-methylbenzoic acid, TPB = 1,2,3,4-tetra-(4-pyridyl)-butane]. Density functional theory (DFT) calculations were carried out to investigate the nature of intermolecular interactions between BMBA and TPB. The cooperation between hydrogen bond and halogen bond in building up the open organic architecture was demonstrated elaborately. Complex 1 exhibits strong photoluminescence and high thermal stability. The nature of electronic transitions in the photoluminescent process was investigated by means of time-dependent DFT (TDDFT) calculations and molecular orbital analyses, revealing that the luminescent property of the helical supramolecular architecture of 1 was ligand-based. Periodic DFT calculations show that 1 is an electrical insulator with a band gap of 3.29 eV. A novel two-dimensional, layered, helical supramolecular architecture driven by hydrogen and halogen bonds cooperatively was synthesized and characterized. The material exhibited strong photoluminescence and high thermal stability. Experimental results have been fully rationalized via DFT and TDDFT calculations.

Novel thermally activated delayed fluorescence (TADF) host materials for blue electrophosphores-cence were designed by combining the electron acceptor dibenzothiophene (DBT) unit and the electron donor acridine derivatives into a single molecular unit by density functional theory (DFT). Depending on the optimal charge transfer, DFT and time-dependent DFT (TD-DFT) calculations for the ground state were performed to obtain the energy of the singlet (S1) and triplet (T1) excited states of the TADF material for Hartree-Fock percentage of TD-DFT. The sufficiently large separation between the HOMO and LUMO resulted in a small difference in energy (ΔEST) between the S1 and T1 states using DFT and TD-DFT calculations. The host molecules retained high triplet energy and showed great potential for use in blue organic light-emitting diodes (OLED). The results showed that these molecules are a good TADF host materials because they have a low barrier to hole and electron injection with a balanced charge transporting property for both holes and electrons, and a small ΔEST.