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  • [2 + 2] Cycloaddition Produces Divalent Organic Color-Centers with Reduced Heterogeneity in Single-Walled Carbon Nanotubes
Title: [2 + 2] Cycloaddition Produces Divalent Organic Color-Centers with Reduced Heterogeneity in Single-Walled Carbon Nanotubes
Organic color centers (OCCs), generated by the covalent functionalization of single-walled carbon nanotubes, have been exploited for chemical sensing, bioimaging, and quantum technologies. However, monovalent OCCs can assume at least 6 different bonding configurations on the sp2 carbon lattice of a chiral nanotube, resulting in heterogeneous OCC photoluminescence emissions. Herein, we show that a heat-activated [2 + 2] cycloaddition reaction enables the synthesis of divalent OCCs with a reduced number of atomic bonding configurations. The chemistry occurs by simply mixing enophile molecules (e.g., methylmaleimide, maleic anhydride, and 4-cyclopentene-1,3-dione) with an ethylene glycol suspension of SWCNTs at elevated temperature (70–140 °C). Unlike monovalent OCC chemistries, we observe just three OCC emission peaks that can be assigned to the three possible bonding configurations of the divalent OCCs based on density functional theory calculations. Notably, these OCC photoluminescence peaks can be controlled by temperature to decrease the emission heterogeneity even further. This divalent chemistry provides a scalable way to synthesize OCCs with tightly controlled emissions for emerging applications.  more » « less
Award ID(s):
2204202 1944921
PAR ID:
10552095
Author(s) / Creator(s):
; ; ; ; ; ; ;
Publisher / Repository:
ACS
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
146
Issue:
33
ISSN:
0002-7863
Page Range / eLocation ID:
23582-23590
Subject(s) / Keyword(s):
carbon nanotubes, cyclization, functionalization, quantum defects, organic color centers
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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