Search results for "iTED"
showing 10 items of 2408 documents
Understanding and exploiting long-lived near-infrared emission of a molecular ruby
2018
Coordination chemistry reviews 359, 102 - 111 (2018). doi:10.1016/j.ccr.2018.01.004
Excited State Tuning of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores by Push-Pull Effects and Bite Angle Optimization: A Comprehensive Exp…
2013
The synergy of push-pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the (1) MLCT absorption and the (3) MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the (3) MLCT excited-state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd-NH2 )(EtOOC-tpy)][PF6 ]2 , [Ru(ddpd){(MeOOC)3 -tpy}][PF6 ]2 , and [Ru(ddpd-NH2 ){(EtOOC)3 -tpy}][PF6 ]2 the combination of the electron-accepting 2,2';6',2''-terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron-donating N,N'-dimethyl-N,N'-dipyridin-2-ylpyridin…
EXTENDED HÜCKEL MOLECULAR ORBITAL CALCULATION OF THE TEMPERATURE DEPENDENCE OF THE QUADRUPOLE SPLITTING OF [Fe(H2O)6] SiF6 AND KFeCl3
1976
A number of papers have appeared in which the temperature dependence of the quadrupole splitting has been treated, whereby covalency effects have been considered by introducing the orbital reduction factor k, with k ranging from 1.-0.7. There are, however, two problems : (1) k is unisotropic if the symmetry is lower than cubic, (2) the spin orbit coupling of the ligand electrons are usually neglected. These two problems have been treated here by using SCCEHMO [1] calculations on two examples, [Fe(H2O)6]SiF6 and KFeCl3, which have been previously delt with by other authors using ligand field theory [2, 3]. For both compounds the differences between the measured and the calculated quadrupole …
Thermal and optical switching of bistable iron compounds and possible applications
1993
Abstract Iron(II) coordination compounds with ligand field strengths close to the mean spin pairing energy may undergo thermal spin transition in the solid as well as in the liquid state. The thermodynamically stable state is high spin (HS) 5T2 (under Oh symmetry) with (t2)4 e2 electron configuration above the critical transition temperature Tc, and low spin (LS) 1A1 with (t2)6 electron configuration below Tc. The spin transition curve γHS(T) (molar fraction of HS molecules as function of temperature) can be abrupt or gradual, with or without hysteresis, or even with a plateau near Tc. Tc itself can vary over the whole temperature scale between the liquid helium region up to above room temp…
Metastable electronic states induced by nuclear decay and light
1994
Radioactive atoms incorporated in insulating solid-state compounds create various kinds of chemical and physical “after-effects” upon nuclear disintegration. Mossbauer emission spectroscopy of57Co-labelled coordination compounds has undoubtedly become the most informative technique to detect such after-effects like aliovalent charge and spin states of the nucleogenic iron atom resulting from the57Co(EC)57Fe decay, low energy excitations of crystal field and Zeeman states, linkage isomerism, radical formation with subsequent redox reactions, and others. We have extensively studied57Co-labelled complexes with [CoIIN6] cores employing time-integral and time-resolved Mossbauer emission spectros…
Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry.
2021
In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes and the resulting non-emissive low-energy metal-centered states. Low-energy excited states decay efficiently non-radiatively, so that near-infrared emissive transition metal complexes with 3d transition metals are even more challenging. We report that the heteroleptic pseudo-octahedral d2-vanadium(iii) complex VCl3(ddpd) (ddpd = N,N′-dimethyl-N,N′-dipyridine-2-yl-pyridine-2,6-diamine) shows near-infrared singlet → triplet spin–flip phosphorescence maxima at 1102, 1219 and 1256 nm with a …
A Heteroleptic Push-Pull Substituted Iron(II) Bis(tridentate) Complex with Low-Energy Charge-Transfer States
2014
A heteroleptic iron(II) complex [Fe(dcpp)(ddpd)](2+) with a strongly electron-withdrawing ligand (dcpp, 2,6-bis(2-carboxypyridyl)pyridine) and a strongly electron-donating tridentate tripyridine ligand (ddpd, N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) is reported. Both ligands form six-membered chelate rings with the iron center, inducing a strong ligand field. This results in a high-energy, high-spin state ((5) T2 , (t2g )(4) (eg *)(2) ) and a low-spin ground state ((1) A1 , (t2g )(6) (eg *)(0) ). The intermediate triplet spin state ((3) T1 , (t2g )(5) (eg *)(1) ) is suggested to be between these states on the basis of the rapid dynamics after photoexcitation. The low-energy …
ChemInform Abstract: Excited State Decay of Cyclometalated Polypyridine Ruthenium Complexes: Insight from Theory and Experiment
2016
Deactivation pathways of the triplet metal-to-ligand charge transfer (3MLCT) excited state of cyclometalated polypyridine ruthenium complexes with [RuN5C]+ coordination are discussed on the basis of the available experimental data and a series of density functional theory calculations. Three different complex classes are considered, namely with [Ru(N^N)2(N^C)]+, [Ru(N^N^N)(N^C^N)]+ and [Ru(N^N^N)(N^N^C)]+ coordination modes. Excited state deactivation in these complex types proceeds via five distinct decay channels. Vibronic coupling of the 3MLCT state to high-energy oscillators of the singlet ground state (1GS) allows tunneling to the ground state followed by vibrational relaxation (path A…
Excited-state lifetimes of [Fe (bipy)3]2+ and [Fe(phen)3]2+
1990
Abstract In the low-spin [Fe(bipy)3]2+ (bipy = 2,2′,bipyridine) and [Fe(phen)3]2+ (phen = 1,10-phenanthroline) complexes an excited high-spin 5T2 ligand field state can be populated by irradiating into the 1MLCT absorption band at 530 nm. The lifetimes of this excited state at low temperatures are reported for [Fe(bipy)3]2+ doped into [Zn(bipy)3] (PF6)2 and [Zn(bipy)3] (BF4)2 and for [Fe(phen)3]2+ and [Fe(bipy)3]2+ embedded in the ion exchange polymer Nafion. For [Fe(bipy)3]2+ in [Zn(bipy)3](PF6)2 the observed lifetimes decrease from 1600 ns at 10 K to 14 ns at 125 K.
He-I and He-II excited photoelectron spectra of cyclohepttatrienetricarbonyl complexes of group via metals
1979
Abstract Photoelectron spectra of Group VIA metal complexes M(CO) 3 (η 6 -C 7 H 8 ) have been assigned using experimental criteria along with quantum-mechanical calculations. A general agreement between computed and measured ionization energies has been found for molecular orbitas mainly ligand in character. Similar correlations do not hold for the highest orbitals, mainly metal d based. The energies associated with ionization processes are, in this case, largely dominated by the relaxation terms. The variations of intensities of these bands on changing the energy of ionizing radiation were of crucial significance in the assignment