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Peer-reviewedCC BY 4.0Chemistry (Weinheim an Der Bergstrasse, Germany)

Coordination Chemistry of Boron Subphthalocyanine With BINOL Derivatives: Unexpected Oxidation to Oxa[4]Helicene and Properties of the Resulting Axially Coordinated Complexes Containing Oxa[4]Helicene and/or BINOL Derivatives

  • Shafikul Islam1,2
  • Kazuyuki Asahi3
  • Hiroyuki Nishikawa3
  • Daiki Tauchi4
  • Masashi Hasegawa4
  • Ken‐ichi Sugiura1
4 affiliations
  1. 1Department of Chemistry, Graduate School of Science Tokyo Metropolitan University Hachi‐Oji Tokyo Japan
  2. 2Department of Chemistry Jahangirnagar University Dhaka Bangladesh
  3. 3Graduate School of Science and Engineering Ibaraki University Mito Ibaraki Japan
  4. 4Department of Chemistry, Graduate School of Science Kitasato University Sagamihara Kanagawa Japan
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Abstract

In the course of our research on axially coordinated metalloporphyrinoids with stable bonding based on the hard and soft acid–base (HSAB) theory, we focused on boron subphthalocyanine because of the hard acid character of the boron(III) center. 1,1′‐Bi‐2‐naphthol (BINOL) was selected as an axial ligand to introduce chirality into the otherwise achiral subphthalocyanine. Surprisingly, treatment of unsubstituted BINOL with boron subphthalocyanine resulted in the formation of a complex coordinated to an oxa[4]helicene derivative formed via a ring‐closure reaction of BINOL. In contrast, treatment of the monomethyl ether of BINOL with boron subphthalocyanine afforded the expected axially coordinated complex. Based on several control experiments, we propose a reaction mechanism for the formation of the oxa[4]helicene involving coordination of BINOL, followed by deprotonation and racemization, and subsequent intramolecular ring‐closure via an ionic process. To characterize and elucidate the fundamental properties of the resulting complexes, single‐crystal x‐ray diffraction, NMR spectroscopy, UV–vis absorption spectroscopy, and electrochemical studies were carried out. Furthermore, we investigated the chirality‐derived properties of the complexes, and the chirality‐induced spin selectivity (CISS) effect was evaluated using magnetic conductive atomic force microscopy (mc‐AFM), revealing a large spin polarization.

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Cite

BibTeXRIS
BibTeX
@article{islam2026coordination,
  title = {{Coordination Chemistry of Boron Subphthalocyanine With BINOL Derivatives: Unexpected Oxidation to Oxa[4]Helicene and Properties of the Resulting Axially Coordinated Complexes Containing Oxa[4]Helicene and/or BINOL Derivatives}},
  author = {Shafikul Islam and Kazuyuki Asahi and Hiroyuki Nishikawa and Daiki Tauchi and Masashi Hasegawa and Ken‐ichi Sugiura},
  journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
  year = {2026},
  month = jul,
  doi = {10.1002/chem.71412},
  url = {https://doi.org/10.1002/chem.71412},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Coordination Chemistry of Boron Subphthalocyanine With BINOL Derivatives: Unexpected Oxidation to Oxa[4]Helicene and Properties of the Resulting Axially Coordinated Complexes Containing Oxa[4]Helicene and/or BINOL Derivatives
AU  - Shafikul Islam
AU  - Kazuyuki Asahi
AU  - Hiroyuki Nishikawa
AU  - Daiki Tauchi
AU  - Masashi Hasegawa
AU  - Ken‐ichi Sugiura
PY  - 2026
DA  - 2026/07/25
JO  - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO  - 10.1002/chem.71412
UR  - https://doi.org/10.1002/chem.71412
AB  - In the course of our research on axially coordinated metalloporphyrinoids with stable bonding based on the hard and soft acid–base (HSAB) theory, we focused on boron subphthalocyanine because of the hard acid character of the boron(III) center. 1,1′‐Bi‐2‐naphthol (BINOL) was selected as an axial ligand to introduce chirality into the otherwise achiral subphthalocyanine. Surprisingly, treatment of unsubstituted BINOL with boron subphthalocyanine resulted in the formation of a complex coordinated to an oxa[4]helicene derivative formed via a ring‐closure reaction of BINOL. In contrast, treatment of the monomethyl ether of BINOL with boron subphthalocyanine afforded the expected axially coordinated complex. Based on several control experiments, we propose a reaction mechanism for the formation of the oxa[4]helicene involving coordination of BINOL, followed by deprotonation and racemization, and subsequent intramolecular ring‐closure via an ionic process. To characterize and elucidate the fundamental properties of the resulting complexes, single‐crystal x‐ray diffraction, NMR spectroscopy, UV–vis absorption spectroscopy, and electrochemical studies were carried out. Furthermore, we investigated the chirality‐derived properties of the complexes, and the chirality‐induced spin selectivity (CISS) effect was evaluated using magnetic conductive atomic force microscopy (mc‐AFM), revealing a large spin polarization.
SN  - 0947-6539
SN  - 1521-3765
ER  -