Subtopic Deep Dive

Supramolecular Crystallography
Research Guide

What is Supramolecular Crystallography?

Supramolecular Crystallography studies non-covalent interactions like hydrogen bonds and synthons that govern the assembly of molecules into crystal structures for rational crystal engineering.

This field examines synthons and hydrogen bonding networks in organic solids to design functional materials. Key works include Desiraju's 1995 paper on supramolecular synthons (4777 citations) and the 2001 book on weak hydrogen bonds by Desiraju and Steiner (3761 citations). Over 10,000 papers explore these principles since 1995.

15
Curated Papers
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Key Challenges

Why It Matters

Supramolecular Crystallography enables rational design of pharmaceuticals with controlled polymorphism and materials with tailored optical or mechanical properties. Desiraju (1995) showed synthons predict crystal packing, impacting drug stability (Desiraju and Steiner, 2001). Coordination polymers designed via silver(I) complexes (Khlobystov et al., 2001) yield porous materials for gas storage. Supramolecular isomerism in cobalt complexes (Hennigar et al., 1997) demonstrates tunable frameworks for catalysis.

Key Research Challenges

Predicting Weak Interactions

Accurately modeling C-H···O and weak hydrogen bonds remains difficult due to their subtlety in crystal packing. Desiraju (1996) highlighted structural implications, but computational limits persist (Desiraju and Steiner, 2001). Experimental validation requires high-resolution diffraction.

Controlling Supramolecular Isomerism

Crystallization conditions dictate bilayer vs. open-framework isomers in coordination polymers. Hennigar et al. (1997) showed ligand flexibility in Co complexes leads to multiple outcomes. Reproducible synthesis challenges scale-up (Khlobystov et al., 2001).

Quantifying Non-Covalent Forces

Emerging σ/π-hole and tetrel bonds complicate force hierarchies. Bauzá et al. (2015) and (2013) identified these directional interactions, but their strength relative to hydrogen bonds needs metrics. Halogen behaviors as acceptors add variability (Brammer et al., 2001).

Essential Papers

1.

Supramolecular Synthons in Crystal Engineering—A New Organic Synthesis

Gautam R. Desiraju · 1995 · Angewandte Chemie International Edition in English · 4.8K citations

Abstract A crystal of an organic compound is the ultimate supermolecule, and its assembly, governed by chemical and geometrical factors, from individual molecules is the perfect example of solid‐st...

2.

The Weak Hydrogen Bond

Gautam R. Desiraju, Thomas Steiner · 2001 · Oxford University Press eBooks · 3.8K citations

Abstract The weak hydrogen bond, also known as non-conventional hydrogen bond, has been the subject of intense scrutiny over recent years in several fields, in particular structural chemistry, stru...

3.

The C−H···O Hydrogen Bond:  Structural Implications and Supramolecular Design

Gautam R. Desiraju · 1996 · Accounts of Chemical Research · 1.8K citations

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe C−H···O Hydrogen Bond: Structural Implications and Supramolecular DesignGautam R. DesirajuView Author Information School of Chemistry, University of ...

4.

Supramolecular design of one-dimensional coordination polymers based on silver(I) complexes of aromatic nitrogen-donor ligands

Andrei N. Khlobystov, Alexander J. Blake, Neil R. Champness et al. · 2001 · Coordination Chemistry Reviews · 1.1K citations

5.

Antioxidant activity of curcumin and related compounds

O. P. Sharma · 1976 · Biochemical Pharmacology · 848 citations

6.

Supramolecular Isomerism in Coordination Polymers: Conformational Freedom of Ligands in [Co(NO<sub>3</sub>)<sub>2</sub>(1,2‐bis(4‐pyridyl)ethane)<sub>1.5</sub>]<sub><i>n</i></sub>

Tracy L. Hennigar, Donald C. MacQuarrie, Pierre Losier et al. · 1997 · Angewandte Chemie International Edition in English · 800 citations

Bilayers or open-framework ladder structure? Which supramolecular isomer is formed from Co(NO3)2 and the nonrigid spacer 1,2-bis(2-pyridyl)ethane depends on the crystallization conditions. The open...

7.

The Bright Future of Unconventional σ/π‐Hole Interactions

Antonio Bauzá, Tiddo J. Mooibroek, Antonio Frontera · 2015 · ChemPhysChem · 681 citations

Abstract Non‐covalent interactions play a crucial role in (supramolecular) chemistry and much of biology. Supramolecular forces can indeed determine the structure and function of a host–guest syste...

Reading Guide

Foundational Papers

Start with Desiraju (1995) for synthon concepts (4777 citations), then Desiraju and Steiner (2001) for weak bonds (3761 citations), followed by Desiraju (1996) for C-H···O specifics (1838 citations).

Recent Advances

Study Bauzá et al. (2015) on σ/π-holes (681 citations) and (2013) on tetrel bonds (676 citations) for emerging interactions.

Core Methods

X-ray crystallography reveals networks; synthon analysis predicts packing (Desiraju, 1995); Cambridge Structural Database queries quantify bonds (Desiraju and Steiner, 2001).

How PapersFlow Helps You Research Supramolecular Crystallography

Discover & Search

PapersFlow's Research Agent uses searchPapers and citationGraph on Desiraju (1995) to map 4777 citing works, revealing synthon evolution; exaSearch uncovers niche tetrel bonding papers like Bauzá et al. (2013); findSimilarPapers expands from Desiraju and Steiner (2001) to weak bond databases.

Analyze & Verify

Analysis Agent applies readPaperContent to parse Desiraju (1996) interaction geometries, verifies bond distances via runPythonAnalysis (NumPy for statistical histograms), and uses verifyResponse (CoVe) with GRADE grading to confirm synthon predictions against crystal data; statistical verification quantifies C-H···O bond populations.

Synthesize & Write

Synthesis Agent detects gaps in isomerism control from Hennigar et al. (1997), flags contradictions in halogen acceptor roles (Brammer et al., 2001); Writing Agent uses latexEditText, latexSyncCitations for Desiraju works, latexCompile for packing diagrams, and exportMermaid for hydrogen bond network graphs.

Use Cases

"Analyze hydrogen bond statistics in 50 supramolecular crystals from Desiraju papers."

Research Agent → searchPapers('Desiraju hydrogen bonds') → Analysis Agent → readPaperContent + runPythonAnalysis (pandas bond distance histograms, matplotlib plots) → statistical verification output with GRADE scores.

"Write LaTeX review on synthons with citations from 1995-2020."

Research Agent → citationGraph('Desiraju 1995') → Synthesis Agent → gap detection → Writing Agent → latexEditText + latexSyncCitations + latexCompile → compiled PDF with synthon diagrams.

"Find code for modeling tetrel bonds in crystal structures."

Research Agent → findSimilarPapers('Bauzá tetrel bonding 2013') → Code Discovery → paperExtractUrls → paperFindGithubRepo → githubRepoInspect → Python scripts for σ-hole calculations.

Automated Workflows

Deep Research workflow scans 50+ papers from Desiraju (1995) citationGraph, delivering structured reports on synthon reliability. DeepScan's 7-step chain verifies weak bond claims in Desiraju and Steiner (2001) with CoVe checkpoints and runPythonAnalysis. Theorizer generates hypotheses on σ/π-hole integration from Bauzá et al. (2015).

Frequently Asked Questions

What defines supramolecular crystallography?

It focuses on non-covalent synthons and hydrogen bonds directing molecular assembly into crystals, as defined by Desiraju (1995).

What are key methods?

X-ray diffraction identifies interactions like C-H···O bonds (Desiraju, 1996); computational modeling predicts synthons (Desiraju and Steiner, 2001).

What are seminal papers?

Desiraju (1995, 4777 citations) on synthons; Desiraju and Steiner (2001, 3761 citations) on weak bonds; Hennigar et al. (1997, 800 citations) on isomerism.

What open problems exist?

Predicting isomerism under varying conditions (Hennigar et al., 1997); quantifying tetrel and σ/π-holes (Bauzá et al., 2013, 2015).

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