Jump to main content
Jump to site search

Issue 48, 2018
Previous Article Next Article

Modelling strategies for the covalent functionalization of 2D phosphorene

Author affiliations

Abstract

This paper is a comparative outline of the potential acid–base adducts formed by an unsaturated main group or transition metal species and P atoms of phosphorene (Pn), which derives from black phosphorus exfoliation. Various possibilities of attaining a realistic covalent functionalization of the 2D material have been examined via DFT solid state calculations. The distribution of neighbor P atoms at one side of the sheet and the reciprocal directionalities of their lone pairs must be clearly understood to foreshadow the best possible acceptor reactants. Amongst the latter, the main group BH3 or I2 species have been examined for their intrinsic acidity, which favors the periodic mono-hapto anchoring at Pn atoms. The corresponding adducts are systematically compared with other molecular P donors from a phosphine to white phosphorus, P4. Significant variations emerge from the comparison of the band gaps in the adducts and the naked phosphorene with a possible electronic interpretation being offered. Then, the Pn covalent functionalization has been analyzed in relation to unsaturated metal fragments, which, by carrying one, two or three vacant σ hybrids, may interact with a different number of adjacent P atoms. For the modelling, the concept of isolobal analogy is important for predicting the possible sets of external coligands at the metal, which may allow the anchoring at phosphorene with a variety of hapticities. Structural, electronic, spectroscopic and energy parameters underline the most relevant pros and cons of some new products at the 2D framework, which have never been experimentally characterized but appear to be reasonably stable.

Graphical abstract: Modelling strategies for the covalent functionalization of 2D phosphorene

Back to tab navigation

Supplementary files

Publication details

The article was received on 07 Sep 2018, accepted on 17 Sep 2018 and first published on 12 Nov 2018


Article type: Paper
DOI: 10.1039/C8DT03628D
Citation: Dalton Trans., 2018,47, 17243-17256
  • Open access: Creative Commons BY license
  •   Request permissions

    Modelling strategies for the covalent functionalization of 2D phosphorene

    A. Ienco, G. Manca, M. Peruzzini and C. Mealli, Dalton Trans., 2018, 47, 17243
    DOI: 10.1039/C8DT03628D

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements