title: Two segregated columnar stack platinum-bis-dithiolene molecule solids showing spin-Peierls-type transition above room temperature.
abstract: Two new one-dimensional (1-D) compounds, [CH3-BzPy][Pt(mnt)2] (1) and [CH3-BzPy-d5][Pt(mnt)2] (2) (CH3-BzPy(+) = 1-N-(4-CH3-benzyl)pyridinium and the pyridine in CH3-BzPy(+) was replaced by pyridine-d5 to give the CH3-BzPy-d5(+); mnt(2-) = maleonitriledithiolate), were synthesized and characterized. 1 and 2 show similar magnetic behavior in 1.8-400 K; they experience a spin-Peierls-type transition around 320 K and show a uniform antiferromagnetic S = 1/2 chain behavior in high temperature (HT) phase, a spin gap feature in low temperature (LT) phase. A symmetry breaking structural phase transition is associated with the spin-Peierls-type transition. Two isostructural compounds crystallize in space group P2(1)/c in HT phase, with a = 12.3066(8) Å, b = 27.0522(18) Å, c = 7.4248(4) Å, β = 104.204(6)° and V = 2396.3(3) Å(3) for 1 versus a = 12.3331(9) Å, b = 27.087(4) Å, c = 7.4501(9) Å, β = 104.149(13)° and V = 2413.3(6) Å(3) for 2 at 353 K, while space group P1[combining macron] in LT phase, with a = 7.3203(10) Å, b = 12.2816(16) Å, c = 26.904(4) Å, α = 88.500(4)°, β = 86.731(4)°, γ = 75.421(4)° and V = 2337.0(5) Å(3) for 1 versus a = 7.3308(8) Å, b = 12.2848(13) Å, c = 26.930(3) Å, α = 88.479(3)°, β = 86.652(4)°, γ = 75.563(3)° and V = 2344.5(4) Å(3) for 2 at 296 K. DSC measurements revealed 1 and 2 showing almost the same T(C). This observation is distinction from the [Ni(mnt)2](-)-based spin-Peierls-type analogues [CH3-BzPy][Ni(mnt)2] and [CH3-BzPy-d5][Ni(mnt)2] where the deuteration leads to T(C) up shifting 2.3 K.
authors.affiliation: State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China.
authors.forename: Wei-Hua
authors.initials: WH
authors.lastname: Ning
authors.forename: Xuan-Rong
authors.initials: XR
authors.lastname: Chen
authors.forename: Jian-Lan
authors.initials: JL
authors.lastname: Liu
authors.forename: Hao
authors.initials: H
authors.lastname: Yang
authors.forename: Xiao-Ming
authors.initials: XM
authors.lastname: Ren