Study On Supramolecular Self-assembly Of Aromatic Group Bridged Ureidopyrimidinone Derivatives

Supramolecular polymers play an important role in dynamic materials.The control of the process of supramolecular polymerization is the basis of developing new functions of materials.Previous studies on supramolecular polymerization focused on various physical and chemical methods for regulation,such as acid-base regulation,competitive unit regulation,light regulation,redox regulation and so on.However,there are few reports on the use of single non-covalent interaction to regulate the supramolecular polymerization driven by another non-covalent interaction orthogonally.This thesis focused on the quadruple hydrogen bond-driven supramolecular polymerization that based on aromatic ring-bridged bisureidopyrimidinone(UPy)compounds,using non-covalent interactions to regulate the quadruple hydrogen bonds,such as?-?interaction or metal coordination,etc.,to precisely control the polymerization process of supramolecular polymers.It is to enhance the understanding of the self-assembly laws of various non-covalent interactions and lay the foundation for the development of supramolecular dynamic materials.This thesis is mainly divided into the following three parts:In the first part,we first designed and synthesized p-phenylene group bridged bis-ureidopyrimidinone(UPy)derivatives M1?M3 containing spacers of different lengths(oligopolyethylene glycol),and studied their quadruple hydrogen bonded superamolecular polymerization.The supramolecular polymerization based on ring-chain equilibrium of these molecules were studied by a series of experiments,which showed that the spacer length has a big impact on the ring-opening supramolecular polymerization process.And the main reason for this is the different strengths of?-?interaction between the dioxyphenylene unit and the dimerized UPy motif in the cyclic monomer form.M1 with the shortest spacer lacks this kind of?-?interaction while M3 with the longest spacer possesses a weak?-?interaction,both leading to small value of CPCs.By contrast,M2 with a moderate length of spacer has a strong?-?interaction,resulting in a high CPC value(189 mmol·L^-1).Finally,the host-guest complexation between M1?M3 with the?-electron deficient bipyridinium-based cyclophane“blue-box”were further investigated,which shows that only M3 could perform host-guest complexation.In the second part,we first designed and synthesized a class of UPy derivatives(M4,M5,and M6)with acyclic crown ether spacers,which can undergo supramolecular polymerization through quadruple hydrogen bonds.The spacer of M4 and M5 is a shorter diethylene glycol group,and the spacer of M6 is a longer diethylene glycol group.In the presence of K⁺,the molecular conformation of M4 and M5 changes due to metal coordination,thus forming a stable cyclic dimer.In contrast,due to the longer spacer of M6,only a small part of the molecules can form cyclic dimers.In addition,we also tried to use some other organic and inorganic salts to interact with M6,such as Cs ions and dibenzylamine salts,all of which exhibited certain supramolecular self-assembly effects.In the third part,based on our previous research on ditopic UPy compounds bridged by benzene ring and naphthalene ring,we further designed and synthesized UPy compound M7 bridged by anthracene group with larger?plane.And the self-assembly behavior of M7's quadruple hydrogen bond supramolecular is studied.At the same time,the light-responsive dimerization of anthracycline in M7 was preliminarily studied.