Functional Polymeric Materials Based on Main‐Group Elements

Abstract

The past decade has witnessed tremendous advances in the synthesis of polymers that contain elements from the main groups beyond those found in typical organic polymers. Unique properties that arise from dramatic differences in bonding and molecular geometry, electronic structure, and chemical reactivity, are exploited in diverse application fields. Herein we highlight recent advances in inorganic backbone polymers, discuss how Lewis acid/base functionalization of polymers results in unprecedented reactivity, and survey conjugated hybrids with unique electronic structures for sensor and device applications.

Core and double bond functionalisation of cyclopentadithiophene-phosphaalkenes

“…14). The P1-C1 double bond is 1.678(2) Å, slightly longer (11). cis-4: P1-C1 1.678(2), Si1-C9 1.852(2), Si1-C ipso 1.862(2), 1.867 (2).…”

“…In these building blocks, the low-lying heteroalkene π* orbitals provide an acceptor group resulting in properties applicable to opto-electronic materials. 10,11 The marked difference to its lighter homologue, i.e. the imine derivatives, hold promising developments for the heavier pnictaalkene systems.…”

Small Chains of Main Group Elements by BH3 Adduct Formation of tBu2E‐N(H)‐EtBu2 (E = P, As)

“…[14,15] Oligomers and polymers, in which the main chain is based on elements other than carbon, gained increasing attention in recent years. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] Recent efforts to develop novel oligo-and polymers based on group 13 and 15 elements resulted in the stepwise construction of small chains of pnictogenyl boranes, [35][36][37][38][39] some of them stabilized in the coordination sphere of a transition metal. [11,35,[40][41][42] In analogy to oligomeric phosphanyl-and arsanyl-boranes, 1a and its deprotonated analogue can potentially serve as building blocks for new polymeric materials based on main group elements.…”

Cross-linked porous polyurethane materials featuring dodecaborate clusters as inorganic polyol equivalents

“…This work further showcases how molecular main group chemistry can be harnessed to improve the properties of polymeric materials. [35][36][37][38][39][40][41][42][43][44][45]…”