Cyclometallated platinum(ii) and palladium(ii) complexes containing 1,5-diarylbiguanides: synthesis, characterisation and hydrogen bond-directed assembly†,CrystEngComm

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Cyclometallated platinum(ii) and palladium(ii) complexes containing 1,5-diarylbiguanides: synthesis, characterisation and hydrogen bond-directed assembly†
CrystEngComm ( IF 2.6 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1039/c7ce01805c
Aidan P. McKay _{1,

2,

3,

4} , Georgina E. Shillito _{1,

2,

3,

4} , Keith C. Gordon _{1,

2,

3,

4} , David A. McMorran _{1,

2,

3,

4}

Affiliation

Complexes of the type [M(ppy)(big)], (where M = Pt(II) and Pd(II), ppy is 2-phenylpyridine and big is a 1,5-diarylbiguanide) have been prepared and characterised in solution and in the solid state. The big ligand possesses a DAD triple hydrogen bonding array that is designed to facilitate assembly of the complexes with complementary organic components. In DMF solution and in the solid state, the complexes are found to adopt a syn–syn conformer of the big ligand to allow hydrogen bonding of DMF molecules to pairs of NH donors. DFT calculations correctly predict this conformation, but only when DMF molecules are explicitly included in the calculation. The electronic spectral properties of the Pt(II) complexes are largely independent of the big ligand and are concentration independent in DMF solution, with TD-DFT calculations showing that the emission comes from the [Pt(ppy)] luminophore. In the presence of 1,8-naphthalimide and barbital derivatives, the big ligand adopts the alternate anti–anti conformer, which enables a triple hydrogen bonding motif. Notably, the two components adopt significantly non-planar orientations, a feature which will be important in their use as tectons for rational crystal engineering applications. Complexes of the type [Pd(ppy)(Hbig)]OAc, are also described, where the acetate anion is hydrogen bonded to the protonated Hbig ligand which adopts the anti–anti conformation.

中文翻译：

含1,5-二芳基双胍的环金属化铂（ii）和钯（ii）配合物：合成，表征和氢键定向组装†

制备了[M（ppy）（big）]型的配合物（其中M = Pt（II）和Pd（II），ppy是2-苯基吡啶，big是1,5-二芳基双胍），并在溶液中进行了表征并处于固态。大配体具有DAD三氢键阵列，该阵列设计用于促进复合物与互补有机组分的组装。在DMF溶液中和固态下，发现该络合物采用大配体的syn - syn构象异构体，以允许DMF分子与成对的NH供体进行氢键键合。DFT计算可以正确预测这种构象，但前提是必须在计算中明确包括DMF分子时。Pt（II）的电子光谱性质）络合物在很大程度上不依赖于大配体，并且在DMF溶液中与浓度无关，而TD-DFT计算表明其发射来自[Pt（ppy）]发光体。在存在1,8-萘二甲酰亚胺和巴比妥衍生物的情况下，大配体采用了交替的反-反构象异构体，从而可以实现三重氢键基序。值得注意的是，这两个组件均采用明显的非平面取向，这一特征在用作合理晶体工程应用的构造时将非常重要。类型[钯（PPY）（HBIG）] OAC的复合物，也有记载，其中所述乙酸盐阴离子氢结合到质子化配位体HBIG即采用抗-抗构象。

更新日期：2017-11-16

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