Zhu Xu-Hui, Mercier Nicolas, Frère Pierre, Blanchard Philippe, Roncali Jean, Allain Magali, Pasquier Claude, Riou Amédée
Ingénierie Moléculaire et Matériaux Organiques, UMR-CNRS 6501, Université d'Angers 2 Bd Lavoisier, 49045 Angers, France.
Inorg Chem. 2003 Aug 25;42(17):5330-9. doi: 10.1021/ic034235y.
2,2'-bithiophene derivatives, 5-ammoniumethylsulfanyl-2,2'-bithiophene (AESBT) and 5,5'-bis(ammoniumethylsulfanyl)-2,2'-bithiophene (BAESBT), have been designed for their incorporation in organic-inorganic materials based on iodometalates. Three layered compounds, (BAESBT)PbI(4), (AESBT)(4)Pb(3)I(10), and (AESBT)(3)Bi(2)I(9), have been synthesized as crystals from slowly cooled aqueous solution containing metal halide and bithiophene derivative salts. When starting from the diammonium cation, (BAESBT)PbI(4) hybrid perovskite is obtained. (BAESBT)PbI(4) adopts a triclinic cell (P1) with the lattice parameters a = 8.4741(5) A, b = 8.9255(6) A, c = 16.876(1) A, alpha = 88.328(5) degrees, beta = 81.806(4) degrees, gamma = 88.864(5) degrees, Z = 2. In the structure, PbI(4)(2)(-) perovskite sheets and diammonium cation layers alternate along c. The incorporation of the corresponding monoammonium cation (AESBT) leads to a head to tail arrangement of the molecules in the (AESBT)(4)Pb(3)I(10) hybrid, precluding the formation of the perovskite layers. (AESBT)(4)Pb(3)I(10) is orthorhombic, Pna2(1), with a = 38.333(4) A, b = 22.239(3) A, c = 8.448(2) A, Z = 4. The structure consists of corrugated layers of Pb(3)I(10)(4)(-) separated by organic layers of monoammonium cations. A similar relative situation of molecules in organic layers is observed in (AESBT)(3)Bi(2)I(9), with the inorganic sheets being built up from Bi(2)I(9)(3)(-) entities. (AESBT)(3)Bi(2)I(9) crystallizes in an orthorhombic cell (P2(1)2(1)2(1)) with a = 8.4564(6) A, b = 21.368(2) A, c = 30.747(2) A, Z = 4. In the three compounds, the molecular packings appear different, underlining the interplay between both organic and inorganic components. New packings are stabilized, as illustrated by an original mixed kappa-alpha type arrangement of the bithiophene units in (AESBT)(3)Bi(2)I(9). Furthermore, molecular interactions, especially of S.S type, appear stronger in the hybrids based on the monoammonium cations. The electrical conductivity of a (BAESBT)PbI(4) single crystal has also been investigated, revealing a semiconductive behavior with a characteristic energy of E(g) = 2.535 eV.
已设计出2,2'-联噻吩衍生物5-氨乙基硫烷基-2,2'-联噻吩（AESBT）和5,5'-双（氨乙基硫烷基）-2,2'-联噻吩（BAESBT），用于将其掺入基于碘金属酸盐的有机-无机材料中。通过在含有金属卤化物和联噻吩衍生物盐的缓慢冷却水溶液中合成出三种层状化合物，即(BAESBT)PbI₄、(AESBT)₄Pb₃I₁₀和(AESBT)₃Bi₂I₉的晶体。当从二铵阳离子开始时，可得到(BAESBT)PbI₄杂化钙钛矿。(BAESBT)PbI₄采用三斜晶系（P1），晶格参数为a = 8.4741(5) Å，b = 8.9255(6) Å，c = 16.876(1) Å，α = 88.328(5)°，β = 81.806(4)°，γ = 88.864(5)°，Z = 2。在该结构中，PbI₄²⁻钙钛矿层和二铵阳离子层沿c轴交替排列。相应的单铵阳离子（AESBT）的掺入导致(AESBT)₄Pb₃I₁₀杂化物中分子呈头对尾排列，阻止了钙钛矿层的形成。(AESBT)₄Pb₃I₁₀为正交晶系，Pna2(1)，a = 38.333(4) Å，b = 22.239(3) Å，c = 8.448(2) Å，Z = 4。该结构由Pb₃I₁₀⁴⁻的波纹层组成，由单铵阳离子的有机层隔开。在(AESBT)₃Bi₂I₉中观察到有机层中分子的类似相对情况，无机层由Bi₂I₉³⁻实体构成。(AESBT)₃Bi₂I₉在正交晶系（P2(1)2(1)2(1)）中结晶，a = 8.4564(6) Å，b = 21.368(2) Å，c = 30.747(2) Å，Z = 4。在这三种化合物中，分子堆积情况不同，突出了有机和无机成分之间的相互作用。新的堆积方式得以稳定，如(AESBT)₃Bi₂I₉中联噻吩单元的原始混合κ-α型排列所示。此外，基于单铵阳离子的杂化物中分子间相互作用，尤其是S-S型相互作用，似乎更强。还研究了(BAESBT)PbI₄单晶的电导率，揭示出其具有半导体行为，特征能量E(g) = 2.535 eV。
