Click Chemistry: Versatility and Control in the Hands of Materials Scientists

Abstract

The increasing need for materials with tightly controlled structures will continue to fuel the induction of synthetic organic concepts into materials science. One powerful example is the embracement of “click chemistry” by the materials science community. Because of their high selectivity, near‐perfect reliability, high yields, and exceptional tolerance towards a wide range of functional groups and reaction conditions click reactions have recently attracted increased attention, specifically for use in polymer synthesis as well as for the modification of surfaces and nanometer‐ and mesoscale structures. As outlined in this Review article, click chemistry, such as the CuI‐catalyzed Huisgen 1,3‐dipolar cycloaddition and the Diels–Alder reaction, presents a synthetic concept that lends itself superbly to the controlled preparation of multifunctional materials.

Fluorogenic click reaction

“…1 The Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC) can be considered as a typical ''click'' reaction, in which a 1,2,3-triazole is formed in the presence of Cu(I), allowing very high yields and good regioselectivity. 2,3 It has been widely used in organic synthesis, 4,5 polymer and materials sciences, 6,7 drug development, and bioconjugation chemistry, 8 etc. after its discovery in 2002.…”

Metal-catalyzed azide-alkyne “click” reactions: Mechanistic overview and recent trends

“…This reaction is the catalyzed version of the 1,3 dipolar cycloaddition, known in the former decades as the Huisgen reaction that had already been first disclosed in the XIXth century [25]. The advantages of the Cu(I) catalyzed "click" reaction are that (i) it is regioselective, whereas the non-catalyzed Huisgen reaction lacks regioselectivity, producing both the 1,4-and 1,5-disubstituted isomers, (ii) it proceeds at milder temperature than the non-catalyzed reaction (iii) it fulfills the requirements of "green chemistry" in so far as it can occur in aqueous or alcoholic medium, (iv) the catalyst reported by Sharpless and Fokin is simple and inexpensive; it consists in CuSO 4 •5H 2 O + sodium ascorbate, the later reagent being fine for the reduction of Cu(II) to Cu(I), but not to Cu(0) [22]. The only drawback is the need of large quantities of this catalyst mixture that is slow.…”

“…The concept of "click chemistry" proposed by Kolb, Finn and Sharpless in 2001 [1] has revolutionized molecular engineering including applications to organic and medicinal chemistry [2][3][4][5][6][7][8][9][10][11], polymer science and materials science [12][13][14][15][16][17][18][19][20][21]. Among the various "click" reactions responding to the requirements of this concept, the most generally used one is the copper(I)-catalyzed reaction between terminal alkynes and azides (CuAAC) selectively yielding 1,4-disubstituted 1,2,3-triazoles, that was reported independently by the Sharpless-Fokin [22] and the Meldal groups in 2002 [ 23,24].…”

Click Chemistry‐Based Functionalization on Non‐Oxidized Silicon Substrates

“…[40] The "click" chemistry toolbox includes, for example, ring-opening reactions, thiolene addition, and CuAAC reactions. [41][42][43][44][45] In particular, the CuAAC reaction can be performed under physiological conditions and has found numerous applications in the field of surface chemistry. [45] The upcoming use of silicon-based materials has logically initiated a growing interest in the post-modification of SiÀC-bound organic monolayers by using the click reaction.…”