Naphthalenediimide – A Unique Motif in Macrocyclic and Interlocked Supramolecular Structures

Abstract

This review presents as urvey through macrocyclic andi nterlocked structures containing 1,4,5,8-naphthalendiimide residues from the synthetic point of view and also illustrates the structural particularities that dictate their main applications in supramolecular, biological and materials chemistry. Thep aper is organised as ac omprehensived escription of macrocycles,c yclophanes,c atenanes,r otaxanes and metallamacrocyclesa long with other types of supramolecular interlockeda rchitectures.F or each category,w ep resent the synthetic approach, the structural investigation of their properties and the developed applications as semiconductors, energy storage devices,p hotovoltaics,a rtificial photosystems,sensors,catalysts or molecular machines. 1I ntroduction 2C yclophanes andMacrocycles 3C atenanes andRotaxanes 4M etallamacrocyclic andI nterlocked Structures 5O ther Complex Interlocked Structures 6C onclusions 1I ntroductionArylenediimides (ADIs) are ac lass of aromatic, redox-active compounds showing good thermal, chemical and photochemicals tability that found importanta pplications in various fields ranging from biological chemistry to supramolecular chemistry and materials sciences. [1][2][3][4][5][6][7][8] Pyrromelliticdiimides (PMDIs), naphthalenediimides (NDIs) and perylenediimides (PDIs) are the most studied compounds of this class.Althought he first reports regarding the synthesis and photoelectronic properties of NDI derivatives can be found in the early 1970s, [9] the real potentialo f these compounds was recognized only at the endo f the last century.T he NDI derivatives have lately emerged as the hottest topic among the arylenediimides and became the most investigated in this class. This is reasoned by their enhanced photophysical and redox properties,c omparedt oP MDIsa sw ell as their improved solubility comparedtoP DIs. [6] Structurally,N DI is ap lanar molecule containinga hydrophobic naphthalene core functionalized at positions 1, 4, 5a nd 8w ith twoe lectron-withdrawing imide groups that decrease the charge density on the naphthalene moiety,r esulting in highly acidic p-sur-face.T hese structural elements made NDI an appealing building block for the construction of complex supramoleculara rchitectures associated by p-p stacking, charge-transfer (CT) and van derW aals interactions that involve the naphthalene residue,h ydrogen bonding involving aromatic C-H and C=Og roups,a s well as metal-coordination to the imide groups. [10][11][12][13] N,N-Functionalized NDI derivatives are readily accessible by treatment of 1,4,5,8-naphthalenetetracarboxylic acid dianhydride (NDA) with aliphatic or aromatic amines,i np olars olvents such as DMF or N,Ndimethylacetamide,a th igh temperatures. [14] Simple NDI chromophores display intense absorption bands, in DCM, at wavelengths lower than 400 nm, and weak emission bands,w ith shortS tokes shifts and low quantum yields.M oreover, NDI derivatives have low LUMO energy levels (i.e., À3.7eVf or N,N-dioctylnaphthalenediimide) andc an easily undergo two oneelectronr ev...

Coordination-Directed Construction of Molecular Links

“…In this regard, it provided an early practical tool for the synthesis of catenanes in satisfactory yields and served to further the likelihood of constructing higher-order entangled molecules. − Since the beginning of the millennium, the blossoming of supramolecular-coordination-driven self-assembly involving various noncovalent interactions − has been the basis for assembly of a variety of attractive interpenetrated structures, such as molecular links, rotaxanes, knots, and others. In addition, interlocked molecules with robust covalent skeletons have also been obtained directly through the entwining and threading of organic strands via hydrogen bonding, stacking interactions, anion coordination, or a combination of these noncovalent interactions. − Furthermore, natural interlocked species have been found in biological systems, , such as knotted polynucleotide chains and protein architectures. A number of excellent reviews provide further reading and insights into specific aspects of known examples of interlocked architectures. − …”

Photocatalytic Water Splitting Cycle in a Dye-Catalyst Supramolecular Complex: Ab Initio Molecular Dynamics Simulations

“…The catalytic cycle of the mononuclear WOC [(cy)­Ru II bpy­(H 2 O)] 2+ has been systematically examined by means of a combination of theoretical and experimental techniques and consists of four proton-coupled electron transfer (PCET) steps. − The free energy change of this WOC for each catalytic step from the initial intermediate I 1 to the final intermediate I 0 is reported in Table S1 and Figure S1 in the Supporting Information (SI) . The NDI chromophore family has shown good optical performance in photovoltaics, artificial photosystems, and all-polymer solar cells and potential in achieving photoinduced long-distance charge separation and reducing charge recombination. − In a recent computational work, it has been shown that the NDI dye with diethoxy functional groups considered in this work performs fast electron injection in the TiO 2 semiconductor conduction band on a ps time scale . Furthermore, a very low activation barrier was estimated for the first water oxidation catalytic step upon photooxidation of the molecular photosensitizer (NDI +• ) covalently bound to the Ru-based WOC .…”

Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

“…A second goal was to add crown ethers, that can be reversibly reduced from the neutral to the dianionic state, as these crown ethers become negatively charged upon electrochemical switching and thus are expected to cause a Coulomb attraction between the ammonium axle and the crown ether. The NDI moiety, which is readily applied in various redox-active MIMs, was selected because of its high stability and synthetic accessibility [ 42 ].…”