Neutral Copper(I) Cubane Complexes with Aldehyde Ligands

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Solution Overview

Problem

Current tetra-nuclear neutral copper(I) complexes with a cubane-like structure and phosphine ligands lack sufficient chemical and photophysical stability and properties for optochemical applications, with previous attempts using toxic mercury and negatively charged ligands leading to side reactions and instability.

Innovation Solution

Development of tetra-nuclear neutral copper(I) complexes with phosphine ligands bearing aldehyde or ester groups, which are chemically stable and exhibit good photophysical properties, prepared through methods that avoid toxic substances and maintain a neutral charge, ensuring stability and efficiency.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If amide groups are introduced within the organic residues of bivalent phosphine ligands to improve photophysical properties, then photophysical properties are improved, but undesired side reactions occur and toxic mercury is required

Engineering Contradiction:
Improvephotophysical propertiesVSAvoidside reactions and toxicity
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent changes the chemical parameter of the ligand by replacing amide groups with aldehyde or ester groups. This substitution maintains the ability to improve photophysical properties while eliminating the harmful side reactions and toxic mercury requirements associated with amide-based approaches

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs readily available aldehyde or ester groups that can be easily introduced into phosphine ligands without requiring complex multi-step syntheses or toxic catalysts like mercury, thereby simplifying the preparation process and eliminating harmful factors

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

2Adaptability or versatility

If negatively charged ligands such as 3-(diphenylphosphino)propanoic acid are used, then ligand functionality is enhanced, but the compound forms salts and migrates in electrical fields

Engineering Contradiction:
Improveligand functionalityVSAvoidcharge stability
Core Design Contradiction:
Adaptability or versatilityVSStability of the object's composition

Solution Approach 1:

The patent changes the charge parameter of the ligand from negative to neutral by using aldehyde or ester groups instead of carboxylic acid groups. This maintains ligand functionality while preventing salt formation and migration in electrical fields, thereby improving compositional stability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent converts the potential harm of charged ligands (salt formation, migration) into a benefit by designing neutral ligands with aldehyde or ester groups that provide similar functionality without the adverse effects of charge-related instability

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Adaptability or versatility

If carbonic acid groups are introduced to improve ligand properties, then ligand reactivity is enhanced, but side products are formed

Engineering Contradiction:
Improveligand reactivityVSAvoidside products
Core Design Contradiction:
Adaptability or versatilityVSLoss of substance

Solution Approach 1:

The patent changes the chemical nature of the ligand group from carbonic acid to aldehyde or ester groups. This maintains enhanced ligand reactivity and functionality while avoiding the formation of side products that occurs with carbonic acid groups

Inventive Principle:
Principle #35Parameter changes

Data Source

PatentEP3810619B1Tetra-nuclear neutral copper (i) complexes
Publication Date: 2023.04.26 CLARIANT INT LTD
  • EP3810619B1 patent drawingFigure 1
  • EP3810619B1 patent drawingFigure 2
  • EP3810619B1 patent drawingFigure 3

AI summary

The invention relates to tetra-nuclear neutral copper (I) complexes of Formula (A) that have a cubane-like structure, wherein said complexes comprise phosphine ligands which bear one or more aldehyde or ester groups. Furthermore, the present invention refers to methods for generating such copper (I) complexes of Formula (A) and to uses thereof. Each L is independently from each other a ligand that has a structure of Formula (A1): P(Ar)m(CHR2-CHR1-CO-Y-Rx)n.