DFT vs. TDDFT vs. TDA to simulate phosphorescence spectra of Pt- and Ir-based complexes

A quantum investigation of the optical (mainly luminescence) properties of twelve transition metal complexes using DFT, TDDFT and TDA computations is presented. Unrestricted DFT and TDA outperform TDDFT for the investigated complexes especially when an Ir centre is present.

Люминесценция Pd и Pt бензогидропорфиразинов в ближнем ИК диапазоне

Phosphorescence in the near-IR range under stationary lamp excitation was studied of three palladium and three platinum complexes of benzocondensed hydroporphyrazine phthalocyanine analogues in which molecule one or two isoindole fragments are replaced by a hydrogenated pyrrole ring, giving macrocycles of photosynthetic pigments analogues of chlorin, bacteriochlorin and isobacteriochlorin types. For the first time, the phosphorescence spectra of trans-dibenzotetrahydroporphyrazines (for both platinum and palladium) have been registered, which detection failed during long time due to the record removal of 0-0 bands from the visible area (1.67 and 1.52 µm for Pd and Pt), and also because of the small quantum yield of phosphorescence. The fluorescence of these complexes was also detected.in the near-IR range. On the basis of comparison of experimental results with own and literature data for palladium complexes of a number of tetrapyrroles is shown the approximate additivity of the influence of structural factors — hydrogenation of pyrrole rings, aza- and benzo substitution — on the energy of the lower triplet state T1. The information obtained is essential for targeted creation of emitters in the near-IR range (1.0-1.7 µm).

Quinoline-annulated porphyrin platinum complexes as NIR emitters

The platinum(II) complexes of known quinoline-annulated porphyrins were prepared and spectroscopically characterized. Their optical properties (UV-vis absorption and phosphorescence spectra and phosphorescence lifetimes) were recorded and contrasted against their 2,3-dioxoporphyrin precursor platinum(II) complex. The absorbance and emission spectra (in EtOH glass at 77 K) of the quinoline-annulated porphyrins fall within the NIR optical window of tissue, ranging, depending on the derivative, between [Formula: see text]950 and 1200 nm. The much red-shifted optical spectra, when compared to their non-quinoline-annulated precursors, are attributed to the [Formula: see text]-extension and conformational non-planarity that the annulation causes. The emission yields of the mono-quinoline-annulated derivatives are too low and their lifetimes too short to be practical emitters, but the bis-annulated derivative possesses a practical lifetime and emission yield, suggesting its further exploration, particularly since the methodology toward the solubilization of the quinoline-annulated porphyrins in biological media through derivatization is known.

The mutual noncovalent interactions based on metallophilic cluster and anions: A theoretical investigation of the molecular structure and spectroscopic properties of Host–Guest complexes

The d[Formula: see text] metallophilic host clusters [Au(NHC)2][Formula: see text] [M(CN)2][Formula: see text] [Au(NHC)2][Formula: see text](NHC [Formula: see text] N-heterocyclic carbene, [Formula: see text], Ag) with high phosphorescence are synthesized recently and their phosphorescent modulation by solvents is investigated in theory. In this paper, the guest anions (F−, Cl−, Br−, NO[Formula: see text], and BF[Formula: see text] are used to elucidate their effects on metallophilic interactions and phosphorescence of hosts, and also they served as the probes to study the recognition characters of metallophilic hosts. The calculation shows that the guest anions can mutually interact with the host clusters and further, which can modulate the metallophilic Au[Formula: see text]M distances and the phosphorescence spectra of the hosts.

Manifestations of triplet electronic excitations migration in π-electron containing polymers

The results of spectral studies of polymers with aromatic side groups are considered and analyzed. In particular, the phosphorescence spectra of polyvinylcarbazole (PVCa) polyvinyl-7-benzocarbazole (PV7BK) polypropylcarbazole (PEPC) are presented and analyzed. The phosphorescence of these polymers has been shown to be related to the migration of triplet excitons in macromolecules. The phosphorescence of PVC is determined at 77by deep traps (oxides), at 4.2 -shallow traps (monomer units of PVCa). The spreading length of triplet excitons in PVCa macromolecules is 600 A – that corresponds to the average distances between adjacent traps in the macromolecule. There are no such traps in PV7BK macromolecules. The boundary conditions for triplet excitons in macromolecules of PV7BCa were used for evaluation the excitons spreading length. With this aim the dependence of phosphorescence spectra on molecular weihgt were studied The effect of changing of spectral positions of phosphorescence bands when exciton rich the end macromolecular cell was used. The average trip length of triplet excitons is approximately 1000 A. This distance is in fact limited by the probability of the meeting of triplet excitons in the macromolecule and their annihilation at a given excitation intensity.

Accurate computations to simulate the phosphorescence spectra of large transition complexes: simulated colors match experiment

Herein, an ab initio investigation on the luminescence properties of three iridium(iii) complexes is reported.