Gas-Phase Assembling of Dirhodium Units into a Novel Organometallic Ladder:  Structural and DFT Study

Abstract

A hydrocarbon that has three separate aromatic rings, namely 1,4-bis(p-tolylethyl)benzene (C 24 H 26 ), has been structurally characterized for the first time and tested as an elongated aromatic π-donor in assembling reactions under solvent-free conditions. Its gas-phase interaction with the electrophilic dimetal complex, [Rh 2 (O 2 CCF 3 ) 4 ], affords single crystals of a novel organometallic complex, [Rh 2 (O 2 CCF 3 ) 4 ] 2 ‚(C 24 H 26 ). The product has a ladder type structure built on weak but directional rhodium(II)-π-arene interactions. In the above framework, each C 24 H 26 exhibits a tetradentate-bridging coordination having four rhodium(II) centers attached to the opposite sides of the two peripheral benzene rings. The underlying reasons for such coordination defining the formation of the title product have been discussed based on the results of density functional theory, namely the orbital interaction analysis of the reacting partners.

Probing the binding sites and coordination limits of buckybowls in a solvent-free environment: Experimental and theoretical assessment

“…The deposition technique can utilize a variety of volatile organic donors spanning from planar molecules with isolated multiple carbon-carbon bonds [26] to conjugated planar polyarenes [27] to curved unsaturated -bowls discussed here. As metal-containing units, a number of reactive and volatile complexes can be generally used, but in order to facilitate the formation of metal--arene interactions, the Lewis acidic complexes having one or multiple metal sites open for coordination are preferred.…”

“…We have later demonstrated that the direction of this interaction depends on topology of the frontier molecular orbitals (FMOs) for aromatic ligands and dimetal complexes ( Fig. 9) [8z, 26].…”

Gas phase synthesis and X-ray crystal structures of supramolecular networks with bromocorannulene: Similarities and differences with their corannulene analogs

“…As we have recently illustrated, the topology of the FMOs of reacting partners predetermines coordination of metal centers to specific sites of aromatic ligands [16]. In this regard, the formation of identical local structures is not surprising taking into account similarities between the frontier molecular orbitals (8), Rh1-C10 2.600(9), Rh2-C19 2.598 (8), Rh2-C18 2.582 (9) A.…”

Synthesis and characterizations of a paddlewheel-type dirhodium-based photoactive porous metal-organic framework

“…These functional properties are performed in the solvated or dispersed conditions in the solvent media. Recently, these types of complexes have been utilized as robust building blocks for porous metal-organic frameworks (MOFs) [12][13][14], extended coordination polymers (CPs) [15][16][17][18][19], and supramolecular complexes [20][21]. The merits of a paddlewheel-type dirhodium unit as an MOF building block are (1) the unit's axial site availability, i.e., the open metal site, as a potential site for functional solid-state activities, and (2) the structural robustness compared with other paddlewheel-type dimetal units (such as Cu 2 and Zn 2 ) because of the existence of the Rh\ \Rh single bond.…”