Bis(terpyridine)iron(II) Complex Wires with a Bithiophene Linker for Superior Long-range Electron Transport

Bajpayee, Aayushi; Maeda, Hiroaki; Katagiri, Shunsuke; Sakamoto, Ryota; Nishihara, Hiroshi

doi:10.1246/cl.150519

Cited by 8 publications

(2 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, by appending donor and acceptor groups at the sides of the molecular wire-like oligomeric network bridged by the SCO active sites, spin-state dependence of electron transport could be studied by manipulating the supramolecular system by light or temperature stimulus [67,68]. In another scenario, self-assembled monolayers (SAM) composed of electron acceptor units, electron donor units, and SCO centres could be fabricated on top of a metallic electrode by employing layer by layer (LBL) self-assembly methods, and their electron transfer properties with respect to spin-state could be studied [69][70][71][72][73][74]. Systematic studies in the above discussed challenging directions may lead to interesting results of fundamental and applied scientific importance.…”

Section: Discussionmentioning

confidence: 99%

Spin-crossover in iron(II)-phenylene ethynylene-2,6-di(pyrazol-1-yl) pyridine hybrids: toward switchable molecular wire-like architectures

Kumar¹,

Šalitroš²,

Heinrich³

et al. 2020

J. Phys.: Condens. Matter

View full text Add to dashboard Cite

Luminescent oligo(p-phenylene ethynylene) (OPE) and spin-crossover (SCO) active Fe(II)-2,6-di(pyrazol-1-yl) pyridine (BPP) systems are prominent examples proposed to develop functional materials such as molecular wires/memories. A marriage between OPE and Fe(II)-BPP systems is a strategy to obtain supramolecular luminescent ligands capable of metal coordination useful to produce novel spin-switchable hybrids with synergistic coupling between spin-state of Fe(II) and a physical property associated with the OPE skeleton, for example, electronic conductivity or luminescence. To begin in this direction, two novel ditopic ligands, namely L1 and L2, featuring OPE-type backbone end-capped with metal coordinating BPP were designed and synthetized. The ligand L2 tailored with 2-ethylhexyloxy chains at the 2 and 5 positions of the OPE skeleton shows modulated optical properties and improved solubility in common organic solvents relative to the parent ligand L1. Solution phase complexation of L1 and L2 with Fe(BF4)2·6H2O resulted in the formation of insoluble materials of the composition [Fe(L1)]n(BF4)2n and [Fe(L2)]n(BF4)2n as inferred from elemental analyses. Complex [Fe(L1)]n(BF4)2n underwent thermal SCO centred at T1/2 = 275 K as well as photoinduced low-spin to high-spin transition with the existence of the metastable high-spin state up to 52 K. On the other hand, complex [Fe(L2)]n(BF4)2n, tethered with 2-ethylhexyloxy groups, showed gradual and half-complete SCO with 50% of the Fe(II)-centres permanently blocked in the high-spin state due to intermolecular steric interactions. The small angle x-ray scattering (SAXS) pattern of the as-prepared solid complex [Fe(L1)]n(BF4)2n revealed the presence of nm-sized crystallites implying a possible methodology towards the template-free synthesis of functional-SCO nanostructures.

show abstract

Section: Discussionmentioning

confidence: 99%

Spin-crossover in iron(II)-phenylene ethynylene-2,6-di(pyrazol-1-yl) pyridine hybrids: toward switchable molecular wire-like architectures

Kumar¹,

Šalitroš²,

Heinrich³

et al. 2020

J. Phys.: Condens. Matter

View full text Add to dashboard Cite

show abstract

“…In the past a few decades, the long-range electron transport abilities of molecular wires such as alkyl [1][2][3][4], π-conjugated [5][6][7] and peptide chains [8][9][10][11] have been evaluated on metallic electrodes based on the attenuation factor, β, which is the coefficient in the exponential decay of the electron transfer rate constant depending on the wire length [12]. Our own research has exhibited that bis(terpyridine)metal complex (M(tpy), M = Fe, Co and tpy = 2,2′:6′,2″-terpyridine) wires on gold electrodes have small β values indicating superior long-range electron transport abilities produced by the sequential hopping mechanism [13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%