One‐Dimensional Bromo‐Bridged Ni^III Complexes [Ni(S,S‐bn)₂Br]Br₂ (S,S‐bn=2S,3S‐diaminobutane): Synthesis, Physical Properties, and Electrostatic Carrier Doping

Abstract

A new bromo-bridged Ni III compound has been synthesized. This compound displayed a strong antiferromagnetic interaction between spins located on Ni III species (J=(2350+/-500) K) that result from the strong covalency of the Ni--Br bond and the spin-Peierls transition below 150 K. This was shown by the results of magnetic susceptibility and 81Br nuclear quadrupole resonance spectroscopy analysis. We succeeded in the electrostatic carrier doping of a single crystalline sample by using a field-effect transistor device. This compound also showed n-type semiconductor behavior, which can be reasonably rationalized by the existence of a small amount of Ni II impurities.

Macro- and atomic-scale observations of a one-dimensional heterojunction in a nickel and palladium nanowire complex

“…In particular, quasi-1D halogen-bridged metal complexes (MX-Chains) of the type [M(A) 2 X]Y 2 (M = Ni, Pd, Pt; X = Cl, Br, I; A = e.g., ethylenediamine or 1 R ,2 R -diaminocyclohexane (chxn); Y = e.g., Cl, Br, I, or ClO 4 ) are fascinating materials that exhibit photonic 16 , 17 , magnetic 18 , and electronic properties (Fig. 1 ) 19 – 21 . MX-Chains form a specific isolated 1D electron system composed of the d z 2 orbitals of the metal ions and the p z orbitals of the bridging halide ions.…”

Thermally induced electron–hole dissociation dynamics in quasi-one-dimensional bromo-bridged palladium(iii) Mott-insulator [Pd(en)2Br](Suc-Cn)2·H2O (Cn-Y = dialkylsulfosuccinate; n = 5 and 6)

“…6 It has been known that the averaged-valence (AV) state is stabilized when U is predominant. So far, interesting physical properties have been reported such as gigantic third-order nonlinear optical susceptibility, 3 negative differential electrical conductivity, 4 c electrostatic carrier doping effect, 7 spin-Peierls transition, 8 etc. Mostly, Ni complexes are the target of the study because they show the M 3+ –M 3+ AV state (Mott-insulating state, Fig.…”

Surface Ohmic Conductivity on a Mott Insulator Based on a One‐dimensional Bromide‐bridged Nickel(III) Complex

“…As the Ni MX-Chains tend to have donor levels derived from Ni(II) impurities, they have been reported to act as n-type semiconductors. [25,26] There are several reports of the Ni MX-Chain [Ni(chxn) 2 Br]Br 2 (chxn: (1R,2R)-(À )-1,2-cyclohexanediamine) describing its electrical conductivity, [27][28][29][30] anisotropic conduction, [31] and negative differential resistance in the highvoltage region (bias of more than~20 V). [32] However, its conductivity remains elusive, with orders-of-magnitude (10 À 1 -10 À 5 S cm À 1 ) variations among the reported values.…”

“…Ni MX‐Chains have a strongly correlated electron system ( U > S ), which leads to the AV state of Mott insulators rather than a metallic, MV, or CDW states. As the Ni MX‐Chains tend to have donor levels derived from Ni(II) impurities, they have been reported to act as n‐type semiconductors [25,26] . There are several reports of the Ni MX‐Chain [Ni(chxn) 2 Br]Br 2 (chxn: (1 R ,2 R )‐(−)‐1,2‐cyclohexanediamine) describing its electrical conductivity, [27–30] anisotropic conduction, [31] and negative differential resistance in the high‐voltage region (bias of more than ∼20 V) [32] .…”