Pt(ii)-coordinated tricomponent self-assemblies of tetrapyridyl porphyrin and dicarboxylate ligands: are they 3D prisms or 2D bow-ties?
Pt(ii)-coordinated tricomponent self-assemblies of tetrapyridyl porphyrin and dicarboxylate ligands: are they 3D prisms or 2D bow-ties?
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DOI：
10.1039/d1sc06533e
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发表时间：
2022-04-06
期刊：
影响因子：
8.4
通讯作者：
Saha S
中科院分区：
文献类型：
--
作者：
Benavides PA;Gordillo MA;Yadav A;Joaqui-Joaqui MA;Saha S
热力学上有利于同时协调的Pt（ii）的角落与氮杂和羧酸配体产生三组分配合物与复杂的结构和功能，这需要仔细的结构表征，以准确描绘其结构-功能关系。以前的报道声称cis-（Et 3 P）2 PtII与四吡啶卟啉（M′TPP，M′ = Zn或H2）和二羧酸配体（XDC）的杂配位产生了包含两个水平的M′TPP面和四个由八个Pt（ii）角连接的垂直XDC柱的三维四棱柱，尽管这种结构没有得到它们的1H NMR数据的支持。通过广泛的X射线晶体学和NMR研究，本文中，我们证明了顺式-（Et 3 P）2 Pt II，M′TPP和四种不同的具有不同长度和刚度的XDC连接体的自组装实际上产生了蝴蝶结（蝴蝶结）形状的2D [{cis-（Et 3 P）2 Pt}4（M′TPP）（XDC）2]4+复合物，其特征在于M′TPP核心和两个平行的XDC连接体通过四个杂配位Pt II角而不是3D棱柱连接。这是因为（i）无论它们的长度（π 7-11 π）和刚性如何，XDC连接基通过PtII角分子内桥接M′TPP核心的两个相邻吡啶基-N原子，而不是连接两个共面M′TPP配体;（ii）蝴蝶结复合物在熵上优于棱柱。典型蝴蝶结配合物的富电子ZnTPP核选择性地与高π-酸性的1，4，5，8，9，12-六氮杂苯并菲-2，3，6，7，10，11-六腈形成电荷转移配合物，但不与π-供体如芘形成电荷转移配合物。因此，本工作不仅制备了新型的基于M′ TPP的蝴蝶结配合物并证明了其选择性识别π-酸的能力，而且强调了对超分子组装体进行适当的结构表征以确保其结构-性质关系的准确描述的重要性。热力学上有利于杂配协调的Pt（ii）的角落与四吡啶卟啉和二羧酸配体产生2D领结形的复合物，而不是以前错误的3D tetrahydropyramids棱镜。
Thermodynamically favored simultaneous coordination of Pt(ii) corners with aza- and carboxylate ligands yields tricomponent coordination complexes with sophisticated structures and functions, which require careful structural characterization to paint accurate depiction of their structure–function relationships. Previous reports claimed that heteroleptic coordination of cis-(Et3P)2PtII with tetrapyridyl porphyrins (M′TPP, M′ = Zn or H2) and dicarboxylate ligands (XDC) yielded 3D tetragonal prisms containing two horizontal M′TPP faces and four vertical XDC pillars connected by eight Pt(ii) corners, even though such structures were not supported by their 1H NMR data. Through extensive X-ray crystallographic and NMR studies, herein, we demonstrate that self-assembly of cis-(Et3P)2PtII, M′TPP, and four different XDC linkers having varied lengths and rigidities actually yields bow-tie (⋈)-shaped 2D [{cis-(Et3P)2Pt}4(M′TPP) (XDC)2]4+ complexes featuring a M′TPP core and two parallel XDC linkers connected by four heteroleptic PtII corners instead of 3D prisms. This happened because (i) irrespective of their length (∼7–11 Å) and rigidity, the XDC linkers intramolecularly bridged two adjacent pyridyl-N atoms of a M′TPP core via PtII corners instead of connecting two cofacial M′TPP ligands and (ii) bow-tie complexes are entropically favored over prisms. The electron-rich ZnTPP core of a representative bow-tie complex selectively formed a charge-transfer complex with highly π-acidic 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-heaxacarbonitrile but not with a π-donor such as pyrene. Thus, this work not only produced novel M′TPP-based bow-tie complexes and demonstrated their selective π-acid recognition capability, but also underscored the importance of proper structural characterization of supramolecular assemblies to ensure accurate depiction of their structure–property relationships. Thermodynamically favored heteroleptic coordination of Pt(ii) corners with tetrapyridyl porphyrins and dicarboxylate ligands produces 2D bow-tie shaped complexes instead of previously mischaracterized 3D tetragonal prisms.
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