Noncovalent interactions between organometallic metallocene complexes and single-walled carbon nanotubes

Abstract

First principles density functional pseudopotential calculations have been used to investigate the nature of interactions between single-walled carbon nanotubes (SWNTs) and intercalated transition metal metallocene complexes, M(eta-C(5)H(5))(2) (MCp(2)). Three composites, MCp(2)-graphene (d(t)=infinity), MCp(2)@(17,0) (d(t)=1.33 nm), and MCp(2)@(12,0) (d(t)=0.94 nm) (where M=Fe,Co), have been studied to probe the influence of the nanotube diameter (d(t)) on the nature and magnitude of the interactions. Theoretical results presented here demonstrate that these MCp(2)@SWNT composites are stabilized by weak pi-stacking and CH...pi interactions, and in the case of the CoCp(2)@SWNT composites there is an additional electrostatic contribution as a result of charge transfer from CoCp(2) to the nanotube. The extent of charge transfer (MCp(2)-->SWNT) can be rationalized in terms of the electronic structures of the two fragments, or more specifically, the relative positions of the metallocene highest occupied molecular orbital and the conduction band of the nanotube in the electronic structure of the composite.

Interactions Between Amino Acid‐Tagged Naphthalenediimide and Single Walled Carbon Nanotubes for the Design and Construction of New Bioimaging Probes

“…One of the limitations in the DFT model used is the overestimation of the binding energy caused by weak interactions. [78] This has been first highlighted for the modelling of a supramolecular benzene dimer. [79,78] For this simple aromatic stacking model interaction DFT calculations yielded an inter-ring distance of 3.06 Å and a binding energy of −0.48 eV, whereas higher level modelling (CCSD (T)) calculations gave corresponding values of 4.1 Å and −0.05 eV respectively.…”

“…[78] This has been first highlighted for the modelling of a supramolecular benzene dimer. [79,78] For this simple aromatic stacking model interaction DFT calculations yielded an inter-ring distance of 3.06 Å and a binding energy of −0.48 eV, whereas higher level modelling (CCSD (T)) calculations gave corresponding values of 4.1 Å and −0.05 eV respectively. [79] A similar computational approach was applied hereby (see Supporting Information), and was detailed in a previous publication.…”

Diameter selective electron transfer from encapsulated ferrocenes to single-walled carbon nanotubes

“…12,14,15,18 To further characterize the FeCp 2 encapsulation effect, FeCp 2 @SWCNTs with varying diameters required investigation. In a previous report, SWCNTs produced by the high pressure carbon monoxide (HiPco) method were used as templates for FeCp 2 @SWCNTs.…”

Advances in tailoring the electronic properties of single-walled carbon nanotubes

“…According to the data presented in reports on the experimental and theoretical investigations of the electronic properties of filled SWCNTs, the following substances have an electron donor effect on the nanotubes: molecules -organic molecules (tetrakis(dimethylamino)ethylene (TDAE) and tetrathiafulvalene (TTF) [48,356]) and organometallic molecules (Co(C 5 H 5 ) 2 , Co(C 5 H 4 C 2 H 5 ) 2 [47,399,400], Fe(C 5 H 5 ) 2 [50,260,262,263,265,267,399,400], Ce(C 5 H 5 ) 3 [51,269], M(C 5 H 5 ) 2 , M= V, Cr, Mn, Ni [399]) and simple substances -metals (Ag [46,293,294,296,315,365,401], Cu [293,295], Eu [272,402], Li, K [403], Ti, Zn, Co, Ni, Fe, Mo, Gd, Cu [402,[404][405][406][407][408][409][410]). …”