Kuzniak-Glanowska Emilia, Glosz Dorota, Niedzielski Grzegorz, Kobylarczyk Jedrzej, Srebro-Hooper Monika, Hooper James G M, Podgajny Robert
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland.
Dalton Trans. 2021 Jan 7;50(1):170-185. doi: 10.1039/d0dt03535a. Epub 2020 Dec 8.
The square-planar [PtX] complexes (X = Cl, Br) were successfully incorporated into preprogrammed hybrid organic-inorganic systems, exploiting their expected strong anion-π interactions with π-acidic hexaazaphenylenehexacarbonitrile, HAT(CN). The formation and properties of {[PtCl]; HAT(CN)} aggregates in MeCN solution were evaluated based on their UV-Vis spectra to reveal the approximate binding constant K = 7.9(2) × 10 dm mol, molar absorption coefficient ε = 1.47(2) × 10 dm mol cm, extent of electronic coupling H = 2.18 × 10 cm, and electron delocalization α = 1.75 × 10 (α = 0.13). Strong [PtCl]HAT(CN) interactions in such adducts were also confirmed by the distinct shifts |Δδ| = 0.4 ppm of C NMR peaks, when compared to the π-acid alone. The crystal structures of the resulting (PPh)[PtX][HAT(CN)]·3MeCN (1-Cl and 1-Br) solids are isomorphous with (PPh)[Pt(CN)][HAT(CN)]·3MeCN (1-CN) reported by us previously. The halogenoplatinates occupy exactly the same nodes in the supramolecular network as cyanoplatinate, forming stacked {[PtX];HAT(CN)} columns that are stabilized by [PPh] cations. However, contrary to the pale yellow coloration of the [Pt(CN)]/HAT(CN) systems, currently the dark violet or dark green coloration of solutions and crystalline phases were noted owing to the intense absorption in almost the whole visible region. DFT calculations reproduced the UV-Vis spectroscopic characteristics and linked it with the enhanced charge-transfer of the [PtX]HAT(CN) electronic interactions. Based on the isomorphism of all three (PPh)[PtL][HAT(CN)]·3MeCN congeners we constructed and characterized the unprecedented, first ever anion-π-based binary rod-like core-shell crystalline composites 1-X@1-CN.
通过利用预期的[PtX]（X = Cl、Br）平面四方配合物与π酸性六氮杂苯并六腈（HAT(CN)）之间强烈的阴离子-π相互作用，成功地将其纳入预编程的有机-无机杂化体系。基于{[PtCl]; HAT(CN)}聚集体在乙腈溶液中的紫外-可见光谱，对其形成和性质进行了评估，以揭示其近似结合常数K = 7.9(2) × 10³ dm³ mol⁻¹、摩尔吸收系数ε = 1.47(2) × 10⁴ dm³ mol⁻¹ cm⁻¹、电子耦合程度H = 2.18 × 10⁻² cm⁻¹以及电子离域α = 1.75 × 10⁻³（α = 0.13）。与单独的π酸相比，此类加合物中强烈的[PtCl] - HAT(CN)相互作用也通过¹³C NMR峰明显的位移|Δδ| = 0.4 ppm得到证实。所得的(PPh₃)[PtX][HAT(CN)]·3MeCN（1-Cl和1-Br）固体的晶体结构与我们之前报道的(PPh₃)[Pt(CN)₄][HAT(CN)]·3MeCN（1-CN）同构。卤化铂酸盐在超分子网络中占据与氰基铂酸盐完全相同的节点，形成由[PPh₃]阳离子稳定的堆叠{[PtX];HAT(CN)}柱。然而，与[Pt(CN)₄]/HAT(CN)体系的浅黄色不同，由于在几乎整个可见光区域的强烈吸收，目前观察到溶液和晶相呈现深紫色或深绿色。密度泛函理论计算重现了紫外-可见光谱特征，并将其与[PtX] - HAT(CN)电子相互作用增强的电荷转移联系起来。基于所有三种(PPh₃)[PtL][HAT(CN)]·3MeCN同系物的同构性，我们构建并表征了前所未有的、首个基于阴离子-π的二元棒状核壳晶体复合材料1-X@1-CN。
