The Planar Blatter Radical: Structural Chemistry of 1,4‐Dihydrobenzo[e][1,2,4]triazin‐4‐yls

Abstract

Tw oplanarizedanalogues of the prototypical Blatter radical (1), peri-annulated 1 S and 1 O ,a re demonstrated and provideanew platform for molecular and supramolecular engineering,and for tuning electronic and magnetic properties of the radical. Planarization of 1 results in bathochromic shift to the near-IR region, greater spin delocalization, and anodic shift of the reduction potential only for 1 S .M agnetization studies revealed nearly ideal paramagnetic behavior at high temperatures for both radicals 1 S and 1 O with one-dimensional ferromagnetic interaction in the former (2J = 14.4 cm À1 )a nd antiferromagnetic interactions in 1 O at lowt emperatures.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

Auxiliary Atomic Relay Center Facilitates Enhanced Magnetic Couplings in Blatter’s Radical

“…demonstrated the concept of planar Blatter's radical with the synthesis of several functionalized derivatives of planar Blatter's radical by connecting C(8) and C(10) positions with oxygen and sulphur annulation. [39][40][41] As tabulated in last column of 1 unambiguously confirms the modification in the spin density distribution brought about by X-annulation. The decrease in spin density on ring A and ring B for X-Bl as compared to parent Blatter (Bl) reveals that upon X-annulation, the spin density is drained from ring A and B towards ring C in such a way that it results in a transfer of total 10.5% of spin density from benzotriazinyl core (ring A + ring B) to ring C upon O-annulation.…”

New Blatter-type radicals from a bench-stable carbene

“…1 ) 1 is an example of a benzotriazinyl radical with remarkable bench-top stability. Although relatively unexplored since the early report by Blatter in 1968, there has been increased recent interest in this radical and derivatives due to their suitability as building blocks for magnetic materials 2 3 4 5 6 7 8 9 10 11 12 13 , as polymerization initiators 14 15 16 and as ligands in novel radical-metal coordination complexes 17 18 . Related benzotriazines and N-oxide derivatives have seen application in medicinal chemistry, including as anti-cancer drugs, where benzotriazinyl radicals have been proposed as potential DNA-damaging species 19 20 21 22 .…”

Proton-transfer regulated magnetic coupling characteristics in Blatter-based diradicals

“…40 Over the past few years, Koutentis et al introduced various easy synthetic strategies that provide easy access to such superstable Blatter radicals. [41][42][43][44] Although the synthesis of room temperature stable diradicals emerged as a serious challenge to researchers, later on, Gallagher et al succeeded in achieving this milestone by substituting a NN radical with a Blatter's radical, demonstrating thermally robust triple ground state diradicals. 45,46 To generate stable high-spin diradicals, Hutchison and co-workers set an appealing example of scientific endeavour by preparing Blatter radical based m-QDM type and Kekuletype diradicals and demonstrating the applications of Blatter radicals, though the results obtained were contrary to their expectations.…”