Structural and Photophysical Study on Heterobimetallic Complexes with d⁸–d¹⁰ Interactions Supported by Carborane Ligands: Theoretical Analysis of the Emissive Behaviour

Abstract

Heterobimetallic complexes of formula [M{(PPh2)2C2B9H10}(S2C2B10 H10)M'(PPh3)] (M=Pd, Pt; M'=Au, Ag, Cu) and [Ni{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] were obtained from the reaction of [M{(PPh2)2C2B10H10}(S2C2B10H10)] (M=Pd, Pt) with [M'(PPh3)](+) (M'=Au, Ag, Cu) or by one-pot synthesis from [(SH2C2B10H10], (PPh2 )2C2B10H10, NiCl2 ⋅6 H2 O, and [Au(PPh3)](+). They display d(8)-d(10) intermetallic interactions and emit red light in the solid state at 77 K. Theoretical studies on [M{(PPh2)2C2B9H10}(S2C2B10H10)Au(PPh3)] (M=Pd, Pt, Ni) attribute the luminescence to ligand (thiolate, L)-to-"P2-M-S2" (ML') charge-transfer (LML'CT) transitions for M=Pt and to metal (M)-to-"P2-M-S2" (ML') charge-transfer (MML'CT) transitions for M=Ni, Pd.

Linear CuI2Pd0, CuIPd02, and AgI2Pd0 Metal Chains Supported by Rigid N,N′‐Diphosphanyl N‐Heterocyclic Carbene Ligands and Metallophilic Interactions

“…This secondary interaction does not lead to an elongation of the Pd–Cl bond (2.286(1) Å), which remains in the expected range . The Ag I –Pd II bond length (2.8046(5) Å), shorter than the sum of the van der Waals radii (3.35 Å) and comparable to that reported, for example, for the Ag I –Pd II bonds (2.7637(1) and 2.8014(6) Å) in [Mn 2 Pd 2 Ag(μ‐Cl)(μ‐PPh 2 ) 2 (μ‐dppm)(CO) 8 ], indicates d 10 –d 8 –d 10 interactions in 7 …”

“…Despite these potentials, well‐defined Pd n –M m complexes (M=Ag or Cu; n , m small integers) with intermetallic distances below the sum of the van der Waals radii (3.35 and 3.03 Å for Ag and Cu, respectively) appear to be very rare . Examples with Ag I −Pd II (d 10 –d 8 ),– Ag I −Pd 0 (d 10 –d 10 ), Ag I −Pd I (d 10 –d 9 ), Cu II −Pd II (d 9 –d 8 ), Cu I −Pd 0 (d 10 –d 10 ), and Cu I −Pd II (d 10 –d 8 ) interactions have been described, mostly within higher nuclearity clusters.…”

Metal–Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox‐Active Ligands

“…Thep resence of all three components (gold, nickel, and redox-active ligand) appears to be essential for the observed reactivity,a sc onfirmed by control experiments.T his discovery paves the way to novel multimetallic design principles based on redox-active ligand-throughmetal-to-metal electronic communication and non-traditional reactivity with transition metals. [13] Thes tructure shows characteristic metric parameters for the isq À oxidation state for both NO fragments (metric oxidation state (MOS) values of À1.13 AE 0.09), confirming the singlet diradical spin state. Layering asolution of 2 in chloroform with pentane afforded colorless single crystals (see Scheme 1).…”

Unusual Metal–Metal Bonding in a Dinuclear Pt–Au Complex: Snapshot of a Transmetalation Process

“…[19,20] In contrast, very few examples of Pt II →Au I (d 10 ) have been fully characterized. [21][22][23][24] From a structural point of view, several binding modes for the coordination of platinum (II) fragments to Lewis acidic metals are known. The most frequent consists of a metalmetal interaction in which the bond axis lies perpendicular to the coordination plane of the d 8 metal.…”