Rare Guest-Induced Electrical Conductivity of Zn-Porphyrin Metallacage Inclusion Complexes Featuring π-Donor/Acceptor/Donor Stacks
Rare Guest-Induced Electrical Conductivity of Zn-Porphyrin Metallacage Inclusion Complexes Featuring π-Donor/Acceptor/Donor Stacks
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DOI：
10.1021/acsami.3c15959
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发表时间：
2023-12-18
影响因子：
9.5
通讯作者：
Saha，Sourav
中科院分区：
文献类型：
--
作者：
Benavides，Paola A.;Gordillo，Monica A.;Saha，Sourav
共面排列π-给体/受体（π-D/A）阵列之间的电荷转移（CT）相互作用产生了独特的光学和电子特性，这可能有利于（超）分子电子学和能源技术。在此，我们证明了一个具有两个平行的π-供体（4-羧基苯基）- zn -卟啉（ZnTCPP）的四方棱柱形金属-有机笼（MOC18+），选择性地插入平面π-受体客体，如六氮杂三苯基六羰基（HATHCN）、六氮杂三苯基（HCTP）和萘二酰亚胺（NDI）衍生物，形成了具有超分子π-D/ a /D三联体的1:1 πA@MOC18+包合物。嵌入π-受体（HATHCN > HCTP≈ndi）的π-酸度决定了它们与ZnTCPP表面相互作用的性质和强度，进而影响πA@MOC18+包合物的结合亲和度（Ka）和光学电子性质。由于其与ZnTCPP表面的CT相互作用最强，π酸性最强的HATHCN客体具有最大的ka (5 × 106M-1)，竞争性地取代了MOC18+腔中较弱的π受体，并在πA@MOC18+包合物中产生了最高的电导率（2.1 × 10-6S /m）。这项工作证明了πA@MOC18+包合物具有独特的空间电荷传输能力，该包合物具有超分子π-D/ a /D三联态，可以产生可调谐的导电性，这是这种超分子组件罕见但令人垂涎的电子特性，可以进一步扩大其在未来技术中的应用。
Charge-transfer (CT) interactions between co-facially aligned π-donor/acceptor (π-D/A) arrays engender unique optical and electronic properties that could benefit (supra)molecular electronics and energy technologies. Herein, we demonstrate that a tetragonal prismatic metal–organic cage (MOC18+) having two parallel π-donor tetrakis(4-carboxyphenyl)-Zn-porphyrin (ZnTCPP) faces selectively intercalate planar π-acceptor guests, such as hexaazatriphenylene hexacarbonitrile (HATHCN), hexacyanotriphenylene (HCTP), and napthanelediimide (NDI) derivatives, forming 1:1 πA@MOC18+inclusion complexes featuring supramolecular π-D/A/D triads. The π-acidity of intercalated π-acceptors (HATHCN ≫ HCTP ≈ NDIs) dictated the nature and strength of their interactions with the ZnTCPP faces, which in turn influenced the binding affinities (Ka) and optical and electronic properties of corresponding πA@MOC18+inclusion complexes. Owing to its strongest CT interaction with ZnTCPP faces, the most π-acidic HATHCN guest enjoyed the largestKa(5 × 106M–1), competitively displaced weaker π-acceptors from the MOC18+cavity, and generated the highest electrical conductivity (2.1 × 10–6S/m) among the πA@MOC18+inclusion complexes. This work demonstrates a unique through-space charge transport capability of πA@MOC18+inclusion complexes featuring supramolecular π-D/A/D triads, which generated tunable electrical conductivity, which is a rare but much coveted electronic property of such supramolecular assemblies that could further expand their utility in future technologies.