A Remarkable 14‐Nuclear Re V 8 Ag I 6 Coordination Oligomer Derived from a 2D (Re V 2 Ag I 2 ) n Coordination Polymer with d‐ Penicillaminate

Re V polymer/oligomer switching : The aggregation of Re V octahedra, [ReO( d‐ pen‐N,O)( d‐ pen‐N,O,S)] − ( d‐ H 2 pen= d‐ penicillamine), assisted by Ag I ions, leads to the formation of a 2D (Re $\rm{^{{V}}_{{2}}}$ Ag $\rm{^{{I}}_{{2}}}$ ) n coordination polymer 1 , which is converted into a Re $\rm{^{{V}}_{{8}}}$ Ag $\rm{^{{I}}_{{6}}}$ coordination oligomer 2 (see picture; Ag green, S yellow, Re purple, O red, N blue). While 1 results from the self‐assembly of Re $\rm{^{{V}}_{{2}}}$ Ag $\rm{^{{I}}_{{2}}}$ units through AgO coordination bonding, the self‐assembly of Re $\rm{^{{V}}_{{8}}}$ Ag $\rm{^{{I}}_{{6}}}$ molecules in 2 is through COOH⋅⋅⋅OOC hydrogen bonding.