PMID- 37285418
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20230621
LR  - 20230823
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Print)
IS  - 0002-7863 (Linking)
VI  - 145
IP  - 24
DP  - 2023 Jun 21
TI  - Thermally Ultrarobust S = 1/2 Tetrazolinyl Radicals: Synthesis, Electronic 
      Structure, Magnetism, and Nanoneedle Assemblies on Silicon Surface.
PG  - 13335-13346
LID - 10.1021/jacs.3c03402 [doi]
AB  - Open-shell organic molecules, including S = 1/2 radicals, may provide enhanced 
      properties for several emerging technologies; however, relatively few synthesized 
      to date possess robust thermal stability and processability. We report the 
      synthesis of S = 1/2 biphenylene-fused tetrazolinyl radicals 1 and 2. Both 
      radicals possess near-perfect planar structures based on their X-ray structures 
      and density-functional theory (DFT) computations. Radical 1 possesses outstanding 
      thermal stability as indicated by the onset of decomposition at 269  degrees C, based on 
      thermogravimetric analysis (TGA) data. Both radicals possess very low oxidation 
      potentials <0 V (vs. SCE) and their electrochemical energy gaps, E(cell)  approximately  0.9 
      eV, are rather low. Magnetic properties of polycrystalline 1 are characterized by 
      superconducting quantum interference device (SQUID) magnetometry revealing a 
      one-dimensional S = 1/2 antiferromagnetic Heisenberg chain with exchange coupling 
      constant J'/k  approximately  -22.0 K. Radical 1 in toluene glass possesses a long electron 
      spin coherence time, T(m)  approximately  7 mus in the 40-80 K temperature range, a property 
      advantageous for potential applications as a molecular spin qubit. Radical 1 is 
      evaporated under ultrahigh vacuum (UHV) forming assemblies of intact radicals on 
      a silicon substrate, as confirmed by high-resolution X-ray photoelectron 
      spectroscopy (XPS). Scanning electron microscope (SEM) images indicate that the 
      radical molecules form nanoneedles on the substrate. The nanoneedles are stable 
      for at least 64 hours under air as monitored by using X-ray photoelectron 
      spectroscopy. Electron paramagnetic resonance (EPR) studies of the thicker 
      assemblies, prepared by UHV evaporation, indicate radical decay according to 
      first-order kinetics with a long half-life of 50 +/- 4 days at ambient conditions.
FAU - Yang, Zhimin
AU  - Yang Z
AD  - Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304, 
      United States.
FAU - Pink, Maren
AU  - Pink M
AUID- ORCID: 0000-0001-9049-4574
AD  - IUMSC, Department of Chemistry, Indiana University, Bloomington, Indiana 
      47405-7102, United States.
FAU - Nowik-Boltyk, Ewa Malgorzata
AU  - Nowik-Boltyk EM
AUID- ORCID: 0000-0003-3136-4870
AD  - Institute of Physical and Theoretical Chemistry, University of Tubingen, Tubingen 
      72076, Germany.
FAU - Lu, Shutian
AU  - Lu S
AD  - Department of Chemistry, University of Washington, Seattle, Washington 98195, 
      United States.
FAU - Junghoefer, Tobias
AU  - Junghoefer T
AD  - Institute of Physical and Theoretical Chemistry, University of Tubingen, Tubingen 
      72076, Germany.
FAU - Rajca, Suchada
AU  - Rajca S
AD  - Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304, 
      United States.
FAU - Stoll, Stefan
AU  - Stoll S
AUID- ORCID: 0000-0003-4255-9550
AD  - Department of Chemistry, University of Washington, Seattle, Washington 98195, 
      United States.
FAU - Casu, Maria Benedetta
AU  - Casu MB
AUID- ORCID: 0000-0002-5659-7040
AD  - Institute of Physical and Theoretical Chemistry, University of Tubingen, Tubingen 
      72076, Germany.
FAU - Rajca, Andrzej
AU  - Rajca A
AUID- ORCID: 0000-0002-8856-1536
AD  - Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304, 
      United States.
LA  - eng
GR  - R01 GM124310/GM/NIGMS NIH HHS/United States
PT  - Journal Article
DEP - 20230607
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
SB  - IM
PMC - PMC10438971
MID - NIHMS1924984
COIS- The authors declare no competing financial interests.
EDAT- 2023/06/07 19:42
MHDA- 2023/06/07 19:43
PMCR- 2024/06/21
CRDT- 2023/06/07 14:03
PHST- 2024/06/21 00:00 [pmc-release]
PHST- 2023/06/07 19:43 [medline]
PHST- 2023/06/07 19:42 [pubmed]
PHST- 2023/06/07 14:03 [entrez]
AID - 10.1021/jacs.3c03402 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2023 Jun 21;145(24):13335-13346. doi: 10.1021/jacs.3c03402. Epub 
      2023 Jun 7.