Faculty of Chemistry, Jagiellonian University in Krakow, Gronostajowa 2, 30-387 Kraków, Poland.
Institute of Nuclear Physics PAN, Radzikowskiego 152, 31-342 Kraków, Poland.
Molecules. 2022 Jun 26;27(13):4111. doi: 10.3390/molecules27134111.
Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic -metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh)M(CN)·2MeCN (M = Cr, ; Fe, ; Co ; HPG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, - were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)];(HPG)} network features original {[M(CN)];(HPG)} supramolecular -bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)Ar, {[M(CN)];PGH}, between -oriented cyanido ligands of [M(CN)] and resorcinol-like face of HPG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)];PGH}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)] by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.
研究分子共晶型材料对于设计和制备易于吸收的药物、非中心对称和手性光学性能晶体、液晶或塑料相非常重要。从根本上讲，这些研究还为各种超分子合成子和分子有序性提供了有用的信息，包括度量参数、分子匹配、能量层次和组合潜力，通过结构-性能-应用方案吸引了对功能材料的合理设计。阴离子-金属配合物配位配合物的共晶盐得到了适度的探索（与共晶的普遍性相比），在这方面，我们提出了一系列新的同构共晶盐（PPh）[M（CN）]（HPG）·2MeCN（M = Cr，；Fe，；Co ；HPG = 邻苯三酚，1,3,5-三羟基苯）。在这项研究中，使用 SC XRD、Hirshfeld 分析、ESI-MS 光谱、振动 IR 和拉曼、Fe Mössbauer、电子吸收 UV-Vis-NIR 和光致发光光谱以及密度泛函理论计算对进行了实验和理论表征。二维正方形网格状氢键{[M（CN）];（HPG）}网络具有原始的{[M（CN）];（HPG）}超分子 -双（螯合）基元，涉及：（i）两个双循环氢键合成子 M（-CN····HO-）Ar，{[M（CN）];PGH}，在[M（CN）]的氰基配体和间苯三酚样的 HPG 面之间取向，和（ii）两个单氢键 M-CN····HO-Ar，{[M（CN）];PGH}，涉及其余两个氰化物配体。讨论了上述构造基元的出现，以及涉及有机物种、单核配位配合物和多核配合物的 CCDC 数据库中存在的相关数据。物理化学和计算表征揭示了在扩展氢键网络下光谱的显著变化。
