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Published on: February 6, 2020
Controlling Keto-Enol Tautomerism of Ureidopyrimidinone to Generate a Single-Quadruple AADD-DDAA Dimeric Array
Jing Zhang1, Shuaiwei Qi1, Chenyang Zhang1
1State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China.
Abstract:
Units of ureidopyrimidinone (UPy) which dimerize via strong quadruple hydrogen bonding are widely used for the construction of supramolecular systems. This self-complementary system exists in the tautomerism equilibrium of 4[1H]-pyrimidinone dimer and pyrimidin-4-ol dimer, making generated supramolecular assembly systems essentially complicated. In this contribution, a rational but simple design concept is described for preorganizing the self-complementary quadruple hydrogen bonding of UPy via supramolecular strategy into a single-quadruple DDAA-AADD dimeric array. With this concept, the designed UPy derivatives form only 4[1H]-pyrimidinone dimer with a ketone configuration via intermolecular hydrogen-bonding interactions, both in the solid state as well as in solution, as is evident from single-crystal X-ray diffraction and 1H NMR spectroscopy. The single DDAA-AADD dimeric array provides defined noncovalent driving forces that can be used to generate constitutionally clear supramolecular structures that are vitally important in the fields of supramolecular chemistry and materials.
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