Abstract
The review presents an overview of the organic radicals that have been designed and synthesized recently, and their magnetic properties are discussed. The π-conjugated organic radicals such as phenalenyl systems, functionalized nitronylnitroxides, benzotriazinyl, bisthiazolyl, aminyl-based radicals and polyradicals, and Tetrathiafulvalene (TTF)-based H-bonded radicals have been considered. The examples show that weak supramolecular interactions play a major role in modulating the ferromagnetic and antiferromagnetic properties. The new emerging direction of zethrenes, organic polyradicals, and macrocyclic polyradicals with their attractive and discrete architectures has been deliberated. The magnetic studies delineate the singlet-triplet transitions and their corresponding energies in these organic radicals. We have also made an attempt to collate the major organic neutral radicals, radical ions and radical zwitterions that have emerged over the last century.
Highlights
Organic molecules we frequently come across in our daily lives are comprised of closed-shell electronic structures with equal numbers of electrons with up- and down-spins
The paradigm-shifting discovery of the triphenylmethyl radical [2] by Mosses Gomberg in 1900 was a major landmark in the 20th century, which set the stage for studies of molecules with unpaired electrons, i.e., systems with open-shell electronic structures
These novel organic radical systems have initiated a wide range of highly interesting applications in redox-catalysis [7,8], living radical polymerization [9,10,11] and magnetochemistry [12,13], the topic which pertains to this review
Summary
Organic molecules we frequently come across in our daily lives are comprised of closed-shell electronic structures with equal numbers of electrons with up- and down-spins. On the other hand, when, in a molecule comprised of two unpaired electrons, the magnitude of the dipole-dipole interaction is large enough to produce two spin states, i.e., singlet and triplet, it is referred to as a diradical [4,6]. These novel organic radical systems have initiated a wide range of highly interesting applications in redox-catalysis [7,8], living radical polymerization [9,10,11] and magnetochemistry [12,13], the topic which pertains to this review. AA ddiivveerrssee rraannggee ooff oorrggaanniicc nniittrroonnyyllnniittrrooxxiiddee-‐bbaasseedd mmoolleeccuulleess hhaass bbeeeenn ssyynntthheessiizzeedd aanndd tthheeiirr mmaaggnneettiicc pprrooppeerrtiteiesshahvaevbeebeneewnewll setlul dsiteuddbieydsebvyersaelvgerroaulpgs.roWuepws.illWdiescwusisllsodmisceursescesnotmexeamrepcleenst, ewxhaimchplehsa, vwehibcehehnavdeebsiegenneddesbiganseedd boansedsuobntlseubftulencftuionnctailongarlogurpoupmmodoidfiicfiactaiotinosn, s,foforr eexxaammppllee aammiinnoopphheennyyllnniittrroonnyyllnniittrrooxxiiddeess,, hhyyddrrooxxyypphheennyyllnniittrroonnyyllnniittrrooxxiiddeessaannddbbiipphheennyyllnniittrroonnyyllnniittrrooxxidideess
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