Thermochromic Properties of Diphenyl Diselenide in Solution

Synthesis, Structure, Optical Properties and Theoretical Studies of Pt(P−P)(CN)2 with P−P = 1,2‐Bis(diphenylphosphanyl)benzene and 2,2′‐Bis(diphenylphosphanyl)‐1,1′‐binaphthyl − Luminescence from Metal‐to‐Ligand Charge Transfer and Intraligand States

“…Moreover, the emission spectra of both complexes are also rather similar and resemble the phosphorescence of the free binap ligand which, however, is only observed at low temperatures. [14] The IL assignment for the phosphorescence of Pt(binap)(CN) 2 is also supported by the fact that the emission shows a pronounced structure which is typical for the phosphorescence from IL states. [1,15] The phosphorescence of Pt(binap)(CN) 2 appears only in the solid state and is absent in solution.…”

Synthesis, characterization, solvatochromic behavior and crystal structures of complexes [CoIII(salophen)(thioacetamide)2]ClO4 and [CoIII(salophen)(thiobenzamide)2]ClO4

“…These observations may be rationalized based on the assumption that the CT bands are mainly of LLCT character and the electronic transitions occur from the pʌ(C=S) of the coordinated thioacetamid and thiobenzamide to the ʌ* of salophen chelate, mediated by the central Co atom. This is analogous to certain low spin d 6 complexes such as trans-[Co III (acacen)(ta) 2 ]ClO 4 , trans-[Co III ((BA) 2 en)(ta) 2 ]PF 6 [13], Mo(diphos)(CO)(NO)(dtc) [26] and several d 8 Ni(diimine)(dithiolate) [27] and d 10 , Zn(phen)(C 6 H 5 S) 2 [28], Zn(SC 6 H 4 -CH 3 -p) 2 (dic) complexes [29].…”

Photolysis of Isoelectronic Ruthenium Nitrosyl and Diazonium Complexes in Frozen PVC Matrices: Retention of Dinitrogen on Ruthenium Following Photochemical Phenyl Radical Loss

“…[7] Prior to this work, the only examination of the photochemistry of a phenylazo metal complex that we are aware of is the solution photochemistry of RuCl 3 (η 1 -N 2 Ph)(PPh 3 ) 2 performed by Kunkely and Vogler. [8] In this work, it is reported that photolysis of RuCl 3 (η 1 -N 2 Ph)(PPh 3 ) 2 in acetonitrile results in formation of RuCl 3 (NCMe)(PPh 3 ) 2 , N 2 , and biphenyl with Φ = 7 × 10 -3 at λ irr = 520 nm. The proposed mechanism for production of N 2 and biphenyl involves metalto-ligand charge-transfer (MLCT) to the phenylazo ligand resulting in loss of a neutral phenyldiazenyl radical.…”

“…[8] The infrared spectrum exhibits an intense N=N vibrational mode of the diazonium ligand at 1872 cm . [27] Low energy (λ Irr > 590 nm) back-photolysis of the irradiated sample did not result in reversion of the photoproduct to the parent complex, and annealing of the matrix to 160 K resulted only in depletion of the 2170 cm -1 photoproduct absorption with no evidence for reversion to the parent diazonium species.…”

“…[27] Low energy (λ Irr > 590 nm) back-photolysis of the irradiated sample did not result in reversion of the photoproduct to the parent complex, and annealing of the matrix to 160 K resulted only in depletion of the 2170 cm -1 photoproduct absorption with no evidence for reversion to the parent diazonium species. In light of the work of Kunkely and Vogler that established generation of phenyl radicals in the solution photochemistry of RuCl 3 (η 1 -N 2 Ph)(PPh 3 ) 2 , [8] and the results of our low-temperature photolysis experiments demonstrating the formation of a Ruthenium dinitrogen complex following photolysis, we propose photochemical homolysis of the arylazo N-Ph bond to yield a 17-electron RuCl 3 (η 1 -N 2 )(PPh 3 ) 2 and the phenyl radical. Though the phenyl radical has been observed in frozen inert gas matrices, [28,29] we are unable to make any spectral assignments directly attributable to this species in our 85 K PVC matrix experiments.…”