Excited-State Distortion of Rhenium(III) Sulfide and Selenide Clusters

Abstract

The deactivation process for the excited-state decay of hexanuclear rhenium(III) sulfide and selenide clusters, [Re 6 S 8 ] 2+ and [Re 6 Se 8 ] 2+ , has been identified from temperature-dependent photophysical measurements and electronic structure calculations. Plots of ln k nr vs T -1 , where k nr is the nonradiative decay rate constant, yield activation energies for nonradiative energy dissipation ranging from 1221 to 1933 cm -1 , after allowing for low-temperature tunneling. Nonlocal density-functional calculations, with varying proportions of Hartree-Fock exchange, well approximate the experimental 9 K emission maximum of the representative compound (Bu 4 N) 4 [Re 6 S 8 Cl 6 ]. The adiabatic potential energy surface of the luminescent, lowest energy triplet excited state is substantially fixed by symmetry, and the calculations provide quantitative characterization of its features. Notably, the experimental activation energies for a D 4h ( 3 B 1g ) f O h ( 1 A 1g ) excited-state decay process have the same magnitude as zero-point corrected energies of well-defined PES local maxima. The results herein further contribute to rhenium chalcogenide clusters' stature as the most thoroughly characterized luminescent metalmetal bonded clusters known.

Assessment of density functional methods for the study of vanadium and rhenium complexes with thiolato ligands

“…The methodology proposed in this work leads to a deviation of only +0.001, +0.004, and À0.008 Å for Cl À , Br À , and I À , respectively. For the ReAX bonds (X À = Cl À , Br À , I À ), once again the chosen methodology improves the theoretical results previously reported [58,59]. However, the description is not as good as the ones observed for ReARe and ReAS.…”

“…In describing intermetallic ReARe bonds, PBE1PBE/STMIDI underestimates the experimental bond distances by À0.009, À0.015, and À0.020 Å for Cl À , Br À , and I À , respectively, although it is worth noticing that it significantly improves the previous estimations [58,59]. For the ReAS bonds, the employed methodology gives the most astonishing agreement notably improving the results reported by Gray et al [58,59], independent of the employed methodology. The methodology proposed in this work leads to a deviation of only +0.001, +0.004, and À0.008 Å for Cl À , Br À , and I À , respectively.…”

“…For the [Re 6 S 8 X 6 ] 4À hexanuclear clusters, the metal is presented as rhenium(III). Theoretical DFT studies for these anionic clusters have been performed by Gray et al [58,59] employing, HF, BLYP, B3LYP, BP86, and B(24.3HF)P86 and by Arratia-Pérez et al [60]. As discussed in Sections 3.1 and 3.2, PBE1PBE/STMIDI leads to excellent description of ReAS bonds.…”

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

“…[66][67][68][69][70][71] These clusters are prepared in moderate yields from self-assembly reactions of noncluster precursors at elevated temperatures. Hexanuclear rheniumA C H T U N G T R E N N U N G (III) chalcogenide clusters also phosphoresce, [72][73][74][75][76][77][78][79][80] and the totality of Mo II , W II , and Re III clusters (Tc III analogues are known in the solid state [81,82] ) apparently constitute the biggest series of isoelectronic clusters known. The temperature-dependent photophysics of the [Re 6 Q 8 ] 2 + series has been extensively characterized experimentally.…”

Photophysical Properties of a Series of Rhenium Selenide Cluster Complexes Containing Nitrogen‐Donor Ligands

“…[2,3] Later, the luminescence properties of analogous 24-electron rhenium chalcogenide clusters were predicted by Arratia-Pérez [4] and then simultaneously measured and reported by three independent research groups. [15][16][17][18][19][20] In addition, researchers have examined ways to take advantage of these luminescence properties in various applications; examples include oxygen sensors, [21] photocatalysis, [22,23] phosphorescent nanoparticles and hybrid materials, [24][25][26][27][28] clustomesogens, [29][30][31] and hydrogen storage. [15][16][17][18][19][20] In addition, researchers have examined ways to take advantage of these luminescence properties in various applications; examples include oxygen sensors, [21] photocatalysis, [22,23] phosphorescent nanoparticles and hybrid materials, [24][25][26][27][28] clustomesogens, [29][30][31] and hydrogen storage.…”