Molecular crystals cannot be designed like macroscopic objects because they do not assemble according to simple, intuitive rules. Their structure results from the balance of many weak interactions, unlike the strong and predictable bonding patterns found in metal–organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here, we combine computational crystal structure prediction and property prediction to build energy–structure–function maps describing the possible structures and properties available to a candidate molecule. Using these maps, we identify a highly porous solid with the lowest density reported for a molecular crystal. Both crystal structure and physical properties, such as the methane storage capacity and guest selectivity, are predicted using the molecular diagram as the only input. More generally, energy–structure–function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.

By variation of the zinc bonded alkyl group significantly different post-oxygenation products, the novel zinc alkylperoxide and the tetranuclear zinc oxo-encapsulated cluster, were derived from the controlled oxygenation of the corresponding alkylzinc complexes with a pyrrolylketiminate ligand.

The first chiral bipyridyl-type metalloligands based on aluminum derivatives of cinchonine (CN-H) were synthesized and characterized by single-crystal X-ray diffraction studies. These bischelate complexes, (CN)(2)AlX [X = Cl (1a), Me (1b)] were found to be effective building blocks for the preparation of novel helical nanotubular architectures as well as chiral bimetallic coordination polymers, as demonstrated by the rational synthesis of a helical structure formed by 1a and ZnCl(2). The applied methodology stands as an exemplary strategy for the rational synthesis of chiral metal-organic frameworks through self-organization driven by nonbonding interactions or coordination, which could potentially find applications in enantioselective separations and catalysis.

Dedicated to Professor Stanisław Pasynkiewicz on the occasion of his 80th birthdayA particularly demanding task in the area of hybrid organicinorganic materials has been the engineering of well-defined void nanospaces [1] capable of selectively binding a guest molecule to perform a specific function of the system, such as catalysis, [2] storage, [3] or separation.[4] The most common and effective approach to design and prepare metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) of desired topology and functionality is based on coordination-driven self-assembly, and both the correct choice of metal centers and the engineering of the ligands features, such as size, flexibility, and directionality of binding centers, play a decisive role. [5] An additional level of tailorability in the design of these hybrid materials can be achieved by implementation of metalloligands. [5c, 6] Alternatively, soft noncovalent synthesis from simple molecular metal complex-based building blocks could provide a convenient and economic way to construct noncovalent porous materials (NPMs) with a unique guest-responsive framework, [1f, 7] and this approach is one of the major challenges in chemistry. Molecular metal complexes are potentially very attractive as building units for microporous architectures, as relatively weak intermolecular bonding interactions in these supramolecular structures allow the microcavities to conform to the shape or functionality of the guest molecules. However, construction of robust NPMs based on this alternative strategy is still in its infancy and examples of such materials are very rare, [8] which stems from the inherent propensity of molecular crystals to form architectures of maximal density.[9]Recently, we have been focusing on rational design strategies to replace common bipyridines as N-ditopic organic linkers [10] by metal complexes with pyridyl units, namely cinchonine-based metalloligands. Initially we synthesized bischelate aluminum complexes, XAl(CN) 2 (where CN = deprotonated cinchonine), as novel chiral N,N-metalloligands I (Scheme 1), and demonstrated their excellent capability as metallotectons for noncovalent-interaction-driven selfassembly into novel microporous chiral architectures prone to enantioselective sorption, as well as their coordinationdriven self-organization for constructing coordination polymers of helical topology.[11] Herein, we extend this strategy to dinuclear aluminum-cinchone complexes as novel molecular building blocks II to produce flexible homochiral NPMs. We show that the resulting NPMs can compete with classical MOFs as highly selective adsorbents exhibiting unique properties, such as temperature-triggered adsorption as well as very high affinities for H 2 , CO 2 , and CH 4 .A dimethylaluminum derivative of cinchonine, [Me 2 Al(m-CN)] 2 (1), was prepared in high yield by the addition of 1 equiv of AlMe 3 to a slurry of cinchonine (CN-H) in THF (Scheme 2; for experimental details see the Supporting Information). We note that the synthesis and...

The polymer network: The reaction of quinine (QN) with CuI under solvothermal, as well as liquid-assisted grinding, conditions afforded a unique 1D homochiral coordination polymer {[Cu(4)(μ(3)-I)(4)(QN)(2)][Cu(3)(μ(3)-I)(2)(μ(2)-I)(QN)(2)](2)}(n), containing both triangular Cu(3)I(3) and cubane Cu(4)I(4) clusters as connecting nodes (see scheme). Van der Waals interactions between the adjacent 1D polymer chains lead to an extended quasi-honeycomb homochiral pillared 3D network with solvent-free 1D channels.

Previous studies have demonstrated that [(CN)(2)AlCl] and [R(2)Al(μ-CN)](2) (CN=deprotonated cinchonine) complexes can effectively act as chiral, semirigid, N,N-ditopic metalloligands for Zn-containing nodes, and provide viable means for constructing new, homochiral, heterometallic, coordination polymers of zigzag and helical topologies. These findings have prompted further investigations on the organometallic analogues of the formula [(CN)(2)AlR], anticipating their utility as N,N-metalloligands for ZnR(2) units. Surprisingly, reactions of [(CN)(2)AlMe]-type metalloligands with ZnR(2) compounds (R=Me or Et) revealed unprecedented ligand-exchange processes, including zinc-to-aluminium and aluminium-to-zinc transmetalations of alkyl groups. The molecular and crystal structure of the resulting compounds was determined by X-ray diffraction analysis. From the reaction of [(CN)(2)AlMe] with ZnMe(2) a new pseudopolymorphic form of a noncovalent porous material based on [Me(2)Al(μ-CN)](2) molecules was isolated. Strikingly, the analogous reaction involving ZnEt(2) led to the generation of a new chiral 4N-tetratopic heterometalloligand [(CN)EtAl(μ-CN)(2)ZnEt]. The latter unit was successfully connected by alkyl-exchanged ZnMe(2) nodes to give an original homochiral heterometallic {[(CN)EtAl(μ-CN)(2)ZnEt]ZnMe(2)}(n) coordination polymer adopting a snake 1D motif. The outcome of the revealed reactions indicates the complicated multistep reaction route that involves redistribution of cinchonine and alkyl ligands among the Al and Zn centers, and a general reaction scheme is proposed. The results are in strong contrast with the previously studied inorganic-organic [(CN)(2)AlCl/ZnCl(2)] system, which exclusively affords a helical coordination polymer based on ZnCl(2) nodes and (CN)(2)AlCl metalloligands and lacks the exchange of CN ligands.

Dedicated to Professor Stanisław Pasynkiewicz on the occasion of his 80th birthday A particularly demanding task in the area of hybrid organicinorganic materials has been the engineering of well-defined void nanospaces [1] capable of selectively binding a guest molecule to perform a specific function of the system, such as catalysis, [2] storage, [3] or separation. [4] The most common and effective approach to design and prepare metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) of desired topology and functionality is based on coordination-driven self-assembly, and both the correct choice of metal centers and the engineering of the ligands features, such as size, flexibility, and directionality of binding centers, play a decisive role. [5] An additional level of tailorability in the design of these hybrid materials can be achieved by implementation of metalloligands. [5c, 6] Alternatively, soft noncovalent synthesis from simple molecular metal complex-based building blocks could provide a convenient and economic way to construct noncovalent porous materials (NPMs) with a unique guest-responsive framework, [1f, 7] and this approach is one of the major challenges in chemistry. Molecular metal complexes are potentially very attractive as building units for microporous architectures, as relatively weak intermolecular bonding interactions in these supramolecular structures allow the microcavities to conform to the shape or functionality of the guest molecules. However, construction of robust NPMs based on this alternative strategy is still in its infancy and examples of such materials are very rare, [8] which stems from the inherent propensity of molecular crystals to form architectures of maximal density. [9] Recently, we have been focusing on rational design strategies to replace common bipyridines as N-ditopic organic linkers [10] by metal complexes with pyridyl units, namely cinchonine-based metalloligands. Initially we synthesized bischelate aluminum complexes, XAl(CN) 2 (where CN = deprotonated cinchonine), as novel chiral N,N-metalloligands I (Scheme 1), and demonstrated their excellent capability as metallotectons for noncovalent-interaction-driven selfassembly into novel microporous chiral architectures prone to enantioselective sorption, as well as their coordinationdriven self-organization for constructing coordination polymers of helical topology. [11] Herein, we extend this strategy to dinuclear aluminum-cinchone complexes as novel molecular building blocks II to produce flexible homochiral NPMs. We show that the resulting NPMs can compete with classical MOFs as highly selective adsorbents exhibiting unique properties, such as temperature-triggered adsorption as well as very high affinities for H 2 , CO 2 , and CH 4 .A dimethylaluminum derivative of cinchonine, [Me 2 Al(m-CN)] 2 (1), was prepared in high yield by the addition of 1 equiv of AlMe 3 to a slurry of cinchonine (CN-H) in THF (Scheme 2; for experimental details see the Supporting Information). We note that the synthes...

The bimetallic chiral bipyridyl-type metalloligands based on aluminium derivatives of cinchonine, [R(2)Al(μ-CN)](2) (R = Me or Et), in combination with the corresponding ZnR(2) compound as nodes were used for the generation of novel homochiral heterometallic coordination polymers of either zig-zag or helical topology, depending on the character of the R substituent.