Minameyer Martin B, Xu Youzhi, Frühwald Stefan, Görling Andreas, von Delius Max, Drewello Thomas
Department of Chemistry and Pharmacy, Physical Chemistry I, Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.
Institute of Organic Chemistry I, University of Ulm, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
Chemistry. 2020 Jul 17;26(40):8729-8741. doi: 10.1002/chem.202001503. Epub 2020 Jul 1.
[n]Cycloparaphenylenes ([n]CPPs) with n=5, 8, 10 and 12 and their noncovalent ring-in-ring and [m]fullerene-in-ring complexes with m=60, 70 and 84 have been studied by direct and matrix-assisted laser desorption ionization ((MA)LDI) and density-functional theory (DFT). LDI is introduced as a straightforward approach for the sensitive analysis of CPPs, free from unwanted decomposition and without the need of a matrix. The ring-in-ring system of [[10]CPP⊃[5]CPP] was studied in positive-ion MALDI. Fragmentation and DFT indicate that the positive charge is exclusively located on the inner ring, while in [[10]CPP⊃C ] it is located solely on the outer nanohoop. Positive-ion MALDI is introduced as a new sensitive method for analysis of CPP⊃fullerene complexes, enabling the detection of novel complexes [[12]CPP⊃C ] and [[10]CPP⊃C ] . Selective binding can be observed when mixing one fullerene with two CPPs or vice versa, reflecting ideal size requirements for efficient complex formation. Geometries, binding and fragmentation energies of CPP⊃fullerene complexes from DFT calculations explain the observed fragmentation behavior.
已通过直接和基质辅助激光解吸电离（（MA）LDI）以及密度泛函理论（DFT）对具有n = 5、8、10和12的环对亚苯基（[n] CPPs）及其与m = 60、70和84的非共价环中环和[ m ]富勒烯环内配合物进行了研究。LDI被引入作为一种直接的方法，用于对CPPs进行灵敏分析，无需不必要的分解且无需基质。在正离子MALDI中研究了[[10] CPP⊃[5] CPP]的环中环体系。碎片化和DFT表明正电荷仅位于内环上，而在[[10] CPP⊃C ]中，它仅位于外部纳米环上。正离子MALDI被引入作为一种分析CPP⊃富勒烯配合物的新的灵敏方法，能够检测新型配合物[[12] CPP⊃C ]和[[10] CPP⊃C ]。当将一种富勒烯与两种CPPs混合或反之亦然时，可以观察到选择性结合，这反映了有效形成配合物的理想尺寸要求。DFT计算得出的CPP⊃富勒烯配合物的几何结构、结合能和碎片化能解释了观察到的碎片化行为。
