Organometallic complexes as donors and non-fullerene acceptors for organic solar cells: DFT-guided design, structure-property relationships, and future directions.
- 1Department of Chemistry, University of Okara Okara-56300 Pakistan [email protected] [email protected].
Abstract
Computational screening has become indispensable to organic solar cell (OSC) design, allowing the electronic, optical, and charge-transport properties of a candidate to be predicted before synthesis. Organometallic complexes (OMCs) are especially well suited to this approach: their metal centers offer design handles-tunable frontier-orbital energies, strong spin-orbit coupling (SOC), and metal-to-ligand charge-transfer (MLCT) transitions that purely organic semiconductors lack. Long confined to donor and interlayer roles, OMCs have recently emerged as credible non-fullerene acceptors (NFAs) once functionalized with electron-withdrawing groups, yet their donor and acceptor chemistries have been reviewed in isolation rather than within a common density functional theory (DFT) framework. This review examines how DFT and its time-dependent extension (TD-DFT) guide the design of OMCs that function as both donors and NFAs. We assess the prevailing computational protocols-hybrid and range-separated functionals (B3LYP, CAM-B3LYP, ωB97XD, M06-2X), effective core potentials (LANL2DZ), and continuum solvation models (PCM, SMD) and the descriptors that link molecular structure to device performance: frontier molecular orbital (FMO) energies, reorganization and exciton-binding energies, and SOC matrix elements. The literature is organized by metal center-ferrocene (Fe), iridium (Ir), platinum (Pt), ruthenium (Ru), osmium (Os), and metalloporphyrin/phthalocyanine systems. Across the surveyed systems, DFT-computed band gaps reproduce experimental trends well, and an optimal acceptor LUMO window of -3.5 to -3.9 eV emerges. Within this window, we rationalize the record power conversion efficiencies of 19.24% (ternary Pt-based) and 15.25% (ternary Cu-porphyrin) devices. We distill these findings into transferable, metal-specific design rules alongside a candid assessment of method reliability. We close by charting the integration of machine learning with high-throughput DFT toward OMC-NFAs that exceed 20% efficiency with improved operational stability.
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BibTeX
@article{khan2026organometallic,
title = {{Organometallic complexes as donors and non-fullerene acceptors for organic solar cells: DFT-guided design, structure-property relationships, and future directions.}},
author = {Muhammad Usman Khan},
journal = {RSC advances},
year = {2026},
month = oct,
doi = {10.1039/d6ra07089b},
url = {https://europepmc.org/article/MED/42948718},
note = {CC BY},
}
RIS
TY - JOUR
TI - Organometallic complexes as donors and non-fullerene acceptors for organic solar cells: DFT-guided design, structure-property relationships, and future directions.
AU - Muhammad Usman Khan
PY - 2026
DA - 2026/10/27
JO - RSC advances
DO - 10.1039/d6ra07089b
UR - https://europepmc.org/article/MED/42948718
AB - Computational screening has become indispensable to organic solar cell (OSC) design, allowing the electronic, optical, and charge-transport properties of a candidate to be predicted before synthesis. Organometallic complexes (OMCs) are especially well suited to this approach: their metal centers offer design handles-tunable frontier-orbital energies, strong spin-orbit coupling (SOC), and metal-to-ligand charge-transfer (MLCT) transitions that purely organic semiconductors lack. Long confined to donor and interlayer roles, OMCs have recently emerged as credible non-fullerene acceptors (NFAs) once functionalized with electron-withdrawing groups, yet their donor and acceptor chemistries have been reviewed in isolation rather than within a common density functional theory (DFT) framework. This review examines how DFT and its time-dependent extension (TD-DFT) guide the design of OMCs that function as both donors and NFAs. We assess the prevailing computational protocols-hybrid and range-separated functionals (B3LYP, CAM-B3LYP, ωB97XD, M06-2X), effective core potentials (LANL2DZ), and continuum solvation models (PCM, SMD) and the descriptors that link molecular structure to device performance: frontier molecular orbital (FMO) energies, reorganization and exciton-binding energies, and SOC matrix elements. The literature is organized by metal center-ferrocene (Fe), iridium (Ir), platinum (Pt), ruthenium (Ru), osmium (Os), and metalloporphyrin/phthalocyanine systems. Across the surveyed systems, DFT-computed band gaps reproduce experimental trends well, and an optimal acceptor LUMO window of -3.5 to -3.9 eV emerges. Within this window, we rationalize the record power conversion efficiencies of 19.24% (ternary Pt-based) and 15.25% (ternary Cu-porphyrin) devices. We distill these findings into transferable, metal-specific design rules alongside a candid assessment of method reliability. We close by charting the integration of machine learning with high-throughput DFT toward OMC-NFAs that exceed 20% efficiency with improved operational stability.
SN - 2046-2069
ER -