title: From Additivity to Cooperativity in Chemistry: Can Cooperativity Be Measured?
abstract: Cooperative effects can be observed in various research areas in chemistry; cooperative catalysis is well-established, the assembly of compounds on surfaces can be steered by cooperative effects, and supramolecular polymerization can proceed in a cooperative manner. In biological systems, cooperativity is observed in protein-protein, protein-lipid and protein-molecule interactions. Synergistic effects are relevant in frustrated Lewis pairs, organic multispin systems, multimetallic clusters and also in nanoparticles. However, a general approach to determine cooperativity in the different chemical systems is currently not known. In the present concept paper it is suggested that, at least for simpler systems that can be described at the molecular level, cooperativity can be defined based on energy considerations. For systems in which no chemical transformation occurs, determination of interaction energies of the whole system with respect to the interaction energies between all individual component pairs (subsystems) will allow determination of cooperativity. For systems comprising of chemical transformations, cooperativity can be evaluated by determining the activation energy of the synergistic system and by comparing this with activation energies of the corresponding subsystems that lack an activating moiety. For more complex systems, cooperativity is generally determined at a qualitative level.
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Ludger
authors.initials: L
authors.lastname: Tebben
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms Universität Münster, Corrensstraße 40, 48149, Münster, Germany.|Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Mück-Lichtenfeld
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Gustavo
authors.initials: G
authors.lastname: Fernández
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstraße 4, 53115, Bonn, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Armido
authors.identifier: http://orcid.org/0000-0002-1706-513X
authors.initials: A
authors.lastname: Studer
keywords: Hill equation; carbenes; frustrated Lewis pairs; interaction energy; supramolecular chemistry