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Porphene and porphite as porphyrin analogs of graphene and graphite

Journal Article · · Nature Communications
 [1];  [2];  [1];  [1];  [3];  [1];  [4];  [5];  [6];  [2]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences (CAS), Prague (Czech Republic)
  3. Czech Academy of Sciences (CAS), Prague (Czech Republic)
  4. Univ. of Chicago, Lemont, IL (United States)
  5. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  6. Univ. of Colorado, Boulder, CO (United States); Renewable and Sustainable Energy Inst. (RASEI), Boulder, CO (United States)
+ Show Author Affiliations
Two-dimensional materials have unusual properties and promise applications in nanoelectronics, spintronics, photonics, (electro)catalysis, separations, and elsewhere. Most are inorganic and their properties are difficult to tune. Here we report the preparation of Zn porphene, a member of the previously only hypothetical organic metalloporphene family. Similar to graphene, these also are fully conjugated two-dimensional polymers, but are composed of fused metalloporphyrin rings. Zn porphene is synthesized on water surface by two-dimensional oxidative polymerization of a Langmuir layer of Zn porphyrin with K2IrCl6, reminiscent of known one-dimensional polymerization of pyrroles. It is transferable to other substrates and bridges μm-sized pits. Contrary to previous theoretical predictions of metallic conductivity, it is a p-type semiconductor due to a predicted Peierls distortion of its unit cell from square to rectangular, analogous to the appearance of bond-length alternation in antiaromatic molecules. The observed reversible insertion of various metal ions, possibly carrying a fifth or sixth ligand, promises tunability and even patterning of circuits on an atomic canvas without removing any π centers from conjugation.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
Czech Ministry of Education; Czech Science Foundation; Defense Advanced Research Projects Agency (DARPA); National Science Foundation (NSF); US Army Research Laboratory (USARL); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-06CH11357; AC36-08GO28308
OSTI ID:
2204025
Report Number(s):
NREL/JA--5900-87884; MainId:88659; UUID:3131cc12-d879-4b75-8fe6-c8867bc595c2; MainAdminID:70963
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
nanoelectronics
optoelectronics
organic materials
porphene
solar-photochemistry