0000000000202906
AUTHOR
Shilin Yu
Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds
A series of LH[Z–I–Z] halogen(I) complexes, where Z = saccharinato or phthalimido anions and LH = pyridinium, pyrazinium, tetrabutyl (TBA)- or tetramethylammonium (TMA) cations, were prepared, structurally characterized, and discussed as complexes consisting of a [N–I–N]− anion with a three-center–four-electron (3c-4e) halogen bond, and a hydrogen-bonding (pyridinium or pyrazinium) or inert (TBA or TMA) cation. The symmetric [N–I–N]− anion, reminiscent of the triiodide [I–I–I]− anion, is found to be structurally equivalent to its cationic analogue [N–I–N]+ with N–I bond lengths of 2.26 Å. In contrast to the homoleptic [N–I–N]+ complexes, asymmetry of the N–I bond lengths (2.21 and 2.28 Å) w…
Ligand exchange among iodine(I) complexes
A detailed investigation of ligand exchange between iodine(I) ions in [N⋯I⋯N]+ halogen-bonded complexes is presented. Ligand exchange reactions were conducted to successfully confirm whether iodine(I) complex formation, via the classical [N⋯Ag⋯N]+ to [N⋯I⋯N]+ cation exchange reaction from their analogous Ag+ complexes, could be determined solely by using 1H NMR spectroscopy. In instances where the formation of the iodine(I) complex was unclear or in low yield by the traditional cation exchange reaction, a ligand exchange reaction was used to form the desired iodine(I) complexes in a quantitative manner. Mixing two homoleptic [N⋯I⋯N]+ iodine(I) complexes in 1 : 1 ratio was found to undergo a…
Macrocyclic complexes based on [N⋯I⋯N]+ halogen bonds
New 1–2 nm macrocyclic iodine(I) complexes prepared VIA a simple ligand exchange reaction manifest rigid 0.5–1 nm cavities that bind the hexafluorophosphate anion in the gas phase. The size of the cavities and the electrostatic interactions with the iodine(I) cations influence the anion binding properties of these macrocyclic complexes.
A “nucleophilic” iodine in a halogen-bonded iodonium complex manifests an unprecedented I+···Ag+ interaction
Summary When an electron is removed from a halogen atom, it forms a halenium ion X+ (X = I, Br, Cl). In halogen bonding (XB), X+ is considered as a strong XB donor, and when interacting with two XB acceptors (e.g., pyridine), it forms a halonium XB complex with a [N–I–N] three-center-four-electron bond with the two XB acceptors. An unprecedented I+···Ag+ interaction occurs between a [L1–I–L1]+ halogen-bonded complex and a [L2–Ag–L2]+ complex in which the iodonium ion acts like a nucleophile and donates electrons to the silver(I) cation. The X-ray diffraction analysis reveals a short contact [3.4608(3) A] between the I+ and Ag+ cations, and ITC measurements give a ΔG of −6.321 kcal/mol and K…
Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors
Abstract Neutral halogen‐bonded O−I−N complexes were prepared from in situ formed carbonyl hypoiodites and aromatic organic bases. The carbonyl hypoiodites have a strongly polarized iodine atom with larger σ‐holes than any known uncharged halogen bond donor. Modulating the Lewis basicity of the selected pyridine derivatives and carboxylates leads to halogen‐bonded complexes where the classical O−I⋅⋅⋅N halogen bond transforms more into a halogen‐bonded COO−⋅⋅⋅I−N+ ion‐pair (salt) with an asymmetric O−I−N moiety. X‐ray analyses, NMR studies, and calculations reveal the halogen bonding geometries of the carbonyl hypoiodite‐based O−I−N complexes, confirming that in the solid‐state the iodine at…
Macrocyclic complexes based on [N⋯I⋯N]+ halogen bonds
New 1–2 nm macrocyclic iodine(I) complexes prepared VIA a simple ligand exchange reaction manifest rigid 0.5–1 nm cavities that bind the hexafluorophosphate anion in the gas phase. The size of the cavities and the electrostatic interactions with the iodine(I) cations influence the anion binding properties of these macrocyclic complexes. peerReviewed
Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane
We demonstrate the first example of bidirectional reversible electronic energy transfer (REET) between the mechanically bonded components of a rotaxane. Our prototypical system was designed such that photoexcitation of a chromophore in the axle results in temporary storage of electronic energy in a quasi-isoenergetic “reservoir” chromophore in the macrocycle. Over time, the emissive state of the axle is repopulated from this reservoir, resulting in long-lived, delayed luminescence. Importantly, we show that cation binding in the cavity formed by the mechanical bond perturbs the axle chromophore energy levels, modulating the REET process, and ultimately providing a luminescence read-out of c…
Dihypoiodites stabilised by 4-ethylpyridine through O–I–N halogen bonds
Four bis(O–I–N) compounds have been synthesised from various dihypoiodites and 4-ethylpyridine. The compounds were characterised in both the solution and solid states by NMR spectroscopy (1H, 15N), X-ray diffraction, and computational calculations. peerReviewed
CCDC 2068113: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 2105110: Experimental Crystal Structure Determination
Related Article: Eric Kramer, Shilin Yu, Jas S. Ward, Kari Rissanen|2021|Dalton Trans.|50|14990|doi:10.1039/D1DT03324G
CCDC 1966175: Experimental Crystal Structure Determination
Related Article: Kwaku Twum, J. Mikko Rautiainen, Shilin Yu, Khai-Nghi Truong, Jordan Feder, Kari Rissanen, Rakesh Puttreddy, Ngong Kodiah Beyeh|2020|Cryst.Growth Des.|20|2367|doi:10.1021/acs.cgd.9b01540
CCDC 2068107: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 1966174: Experimental Crystal Structure Determination
Related Article: Kwaku Twum, J. Mikko Rautiainen, Shilin Yu, Khai-Nghi Truong, Jordan Feder, Kari Rissanen, Rakesh Puttreddy, Ngong Kodiah Beyeh|2020|Cryst.Growth Des.|20|2367|doi:10.1021/acs.cgd.9b01540
CCDC 2105108: Experimental Crystal Structure Determination
Related Article: Eric Kramer, Shilin Yu, Jas S. Ward, Kari Rissanen|2021|Dalton Trans.|50|14990|doi:10.1039/D1DT03324G
CCDC 2105109: Experimental Crystal Structure Determination
Related Article: Eric Kramer, Shilin Yu, Jas S. Ward, Kari Rissanen|2021|Dalton Trans.|50|14990|doi:10.1039/D1DT03324G
CCDC 2068111: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 2068110: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 1966171: Experimental Crystal Structure Determination
Related Article: Kwaku Twum, J. Mikko Rautiainen, Shilin Yu, Khai-Nghi Truong, Jordan Feder, Kari Rissanen, Rakesh Puttreddy, Ngong Kodiah Beyeh|2020|Cryst.Growth Des.|20|2367|doi:10.1021/acs.cgd.9b01540
CCDC 2068114: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 1966173: Experimental Crystal Structure Determination
Related Article: Kwaku Twum, J. Mikko Rautiainen, Shilin Yu, Khai-Nghi Truong, Jordan Feder, Kari Rissanen, Rakesh Puttreddy, Ngong Kodiah Beyeh|2020|Cryst.Growth Des.|20|2367|doi:10.1021/acs.cgd.9b01540
CCDC 2068106: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 1966172: Experimental Crystal Structure Determination
Related Article: Kwaku Twum, J. Mikko Rautiainen, Shilin Yu, Khai-Nghi Truong, Jordan Feder, Kari Rissanen, Rakesh Puttreddy, Ngong Kodiah Beyeh|2020|Cryst.Growth Des.|20|2367|doi:10.1021/acs.cgd.9b01540
CCDC 2068108: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 2068109: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126
CCDC 2068112: Experimental Crystal Structure Determination
Related Article: Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen|2021|Angew.Chem.,Int.Ed.|60|20739|doi:10.1002/anie.202108126