Ab initio Study on Luminescence and Aurophilicity of a Dinuclear [(AuPH₃)₂(i‐mnt)] Complex (i‐mnt = isomer‐Malononitriledithiolate)

A Theoretical Investigation of Substituent Effects on the Absorption and Emission Properties of a Series of Terpyridylplatinum(II) Acetylide Complexes

“…[41][42][43] We Figure 6. Prediction of the bond length changes between the ground and excited states according to the nodal of the frontier orbitals, taking complex IIa as an example (bond lengths in Å).…”

Theoretical Studies on Metal–Metal Interaction and Intrinsic 1,3[σ*(d)σ(s/p)] Excited States of Dinuclear d10 Complexes with Bridging Phosphane Ligands

“…A similar model has been applied in many studies. [12][13][14][15][16][17]50,51] In this work, we employed the C i symmetry to settle the ground-and excited-state conformations of [M 2 (dpm) 2 ]…”

“…Taking previous studies into account , we found that the M-M distances are linearly correlated with the M-M stretching frequencies for the dinuclear d 10 complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) complexes [Au 2 (dpm) 2 ] 2+ (1), [12,13] [Au 2 (dpm)(i-mnt)] (4), [16] and [(AuPH 3 ) 2 (i-mnt)] (5) [16,17] [dpm = bis(diphosphanyl)-methane and i-mnt = i-malononitriledithiolate]. The results revealed that the 507-nm phosphorescent emission of 1 in acetonitrile has the σ[s(Au 2 )]Ǟσ*[d(Au 2 )] (MC) transition property, [13] while the 512 and 495-nm emissions in the CH 2 Cl 2 solution for 4 and 5, respectively, arise from the Au-Au to i-mnt charge-transfer (MMLCT) transition.…”

“…[1][2][3][4][5] Among these interactions, the Au I -Au I interaction has been intensively investigated both experimentally [6][7][8][9][10][11] and theoretically, [2][3][4][12][13][14][15][16][17] and coined as "aurophilicity" by Schmidbaur. [18] The energy of the aurophilic attraction in the solid state and solution was estimated to be 7-15 kcal/mol, [3] comparable to that of hydrogen bonds.…”

“…The luminescence of Au I complexes was assigned as a metal-centered (MC) transition or a metal-metal-to-ligand charge-transfer (MMLCT) transition. [12][13][14][15][16][17] Recently, we calculated the aurophilic interactions and excited-state properties of model 1050 CIS-optimized structures, the TD-DFT (B3LYP) method was employed to calculate the emission spectra of such complexes. For 3, the phosphorescent emissions were calculated at 424 and 514 nm in the solid state and acetonitrile, which is comparable to the experimental data of 475 and 480 nm, respectively.…”